So you'll end up with one WD 250 GB bootable drive with Windows XP on it, a 4-disk (WD 320 GB blue) RAID0 array used mainly for reading data, and a Samsung 1TB backup drive. But to start you will only mount the boot drive and install to there, then add other drives later.
1. First important question: how many SATA ports does your mobo have, and how are they controlled? Would help if you post the mobo model so we can look at these details. Reason I ask is that, ideally, your boot C: drive should be on the SATA0 channel, and the four RAID0 drives should all be on the same controller. Many mobo's have RAID provided by the on-board chipset, but with limits on how many SATA ports. For example, if your board has 4 SATA ports controlled by the main chipset, plus 2 or 4 more SATA ports controlled by another extra chip, you could have a problem. Putting the boot drive on SATA0 port leaves only 3 more SATA ports on that controller for use in a 4-drive RAID array. Unless your main chipset controller has 5 or more SATA ports, that won't work. Of course, if the extra controller has at least 4 SATA ports on it and it supports RAID0, then you could do what you plan that way.
2. Let's suppose for now that the port count is OK and you can do what you want. You are right to install the OS with only one drive actually installed in the machine. Yes, it normally should be connected to the SATA0 port. Sometimes the wording on the screen can make this confusing. The problem starts with the fact that Windows XP has drivers built in for IDE drives so it can handle them for installation purposes, but it does NOT have built-in drivers for native SATA drives or AHCI mode drives, or RAID. The way Windows itself handles that is to allow you to install the required drivers very early in the Install process - you are offered an option and can choose to install them, but only from a floppy disk! Like you, many don't have that ability. So the mobo makers have provided a nice alternative. Within the BIOS where you set options for disks, for each SATA port you can choose how the port is handled. One good option is IDE Emulation - the BIOS takes over the port and makes it behave exactly like a standard IDE port, so Windows is happy and everything just goes on as planned. But when this option is chosen, often in other BIOS screens you will see that SATA disk as an IDE or as a SCSI disk. Ignore that, and just go ahead and install to your SATA (pretending to be IDE) disk.
3. Once you have XP installed and running, you next want to add four disks for a RAID0 array. They all will need to be hooked up to one controller. Your choices are to use the built-in RAID controller functions of your mobo's chipset (provided there are enough ports), to buy and install a separate RAID controller card for the PCI bus, or to use Windows' RAID system. Obviously the Windows system is simply software-implemented. Most add-on RAID cards, especially the higher-quality (and price) ones will do much or all of the job in their hardware. The system built into the mobo chipset is largely software-based (software is in the BIOS chip itself). Some will tell you hardware-based is the best because it's faster and loads the CPU less, which is important for busy servers. For your case, probably the software-based systems are adequate.
4. The more important questions come from recovery from trouble. There are few standard ways of controlling a RAID array, so every manufacturer has their own way. When failure occurs and you have to change components in the controller side, it's a potential problem. For that reason, some people prefer to use Windows' software system, because it has little dependence on the hardware and we all have faith that Microsoft will maintain backwards compatibility in their RAID implementations. Others choose the add-on hardware card route, arguing that they can simply buy a new add-on card made by the same manufacturer and get it all working perfectly that way. If you choose the built-in mobo RAID system you don't quite have that security because a new mobo with a different chipset maker involved almost certainly will not be able to handle your old disks full of data. There is, however, one important EXCEPTION to that "rule of thumb". I built a system a few years ago using an ABIT mobo that had an nVivia chipset (northbridge and southbridge) including RAID functions. The nVidia company website specifically claimed that they always use the same software algorithms for their built-in RAID and hence any system using their chipset will always handle disks originally written using an earlier nVidia chipset. I set up a RAID1 array on that machine. Last moth I had occasion to check this out - the mobo died, so I searched out and bought a new mobo with features i needed, including an nVidia chipset. Installed and plugged in everything, and Wham! it booted and ran just perfectly, using the RAID1 array disks made on the old system! So that's one example of a way you can protect yourself from hardware failure of the controller section of a RAID array.
When you install a RAID array or whatever type AFTER the OS already is installed on a separate boot disk, you will have to install drivers for it in Windows. However, they do NOT have to be loaded from a floppy drive. Remember to install the right drivers. For example, if you choose to use the mobo's built-in RAID system, follow the instructions that came with your mobo, and don't install drivers for other systems. Subsequently these drivers always will be loaded from the OS boot disk as Windows loads, so that the RAID array can be used. You just can't BOOT from a RAID array installed this way, but that suits your plan just fine.
5. Do NOT attempt to install to a SATA disk on one port, then move it to another. At minimum you'd have to re-adjust BIOS settings for which is the boot drive; I don't know if it would also have trouble finding this moved drive because of Registry settings. You should not have to do this, anyway.
6. You say, "6 SATA on motherboard, not card". MAYBE this means you have six SATA ports all from one controller built into the mobo chipset, which would be no problem. But maybe it means you have 4 on the main chipset, and another 2 from a second separate controller chip. In that case we have the problem of Point #1 above - not enough ports for all your plans. You MIGHT be able to arrange to connect your boot drive to the second controller's port0, install XP to that drive, and set the BIOS to use it as the boot drive. But to do that you WILL have to be able to install a driver for it from floppy disk as an early part of the OS Install. Either borrow or buy a floppy drive for this. That would leave all four SATA ports on the mobo chipset's controller available for the RAID0 array. If this is the route you choose, read all the mobo manual's info carefully. And watch out for driver details. Usually a system like this spends a lot of manual time on how to get the second controller chip to handle two RAID disks connected to its two ports, but it is not clear on how to use those ports as just plain NON-RAID disks. But you should be able to do that.
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