I'm not an expert but here goes:
The two IDE connectors near the floppy connector are the ones you get out-of-the-box from the VIA chipset. These are probably the best ones for a "default" setup, and I think also the least likely to give trouble if you put the boot drive on one of them. With the A7V133 these controllers do support ATA100 - it was only the older A7V board that was limited to ATA66.
The other IDE connectors are controlled by the Promise controller. By default it runs as an additional IDE controller but you can enable Raid0 with a jumper. It's best if you have twin drives for the Raid0 mode, and in fact if you have twins and they're not needed for boot, it might even be better from a performance point of view to use the Raid0 mode. You still have the same disk capacity, only your twins will function as a single, larger, faster disk.
If you are not using the Promise controller, you can disable it in the BIOS settings and it saves time during the boot-up (it will just skip the step where it detects that there are no devices connected). The OSes may still assign it an IRQ, however, but since there are no devices there it won't actually conflict with anything.
As far as hooking up the two disks and two removable drives, I'm interested to hear what advice you get. I have a similar setup except I have a Zip drive instead of a second optical-media drive. I like to have my two hard disks on different IDE channels so they each get their own interrupt. The hard disks are much much faster than either of the removable disks, so I put the two removable disks as slaves on the two IDE channels. I put the CD drive as a slave on the secondary IDE channel so that in situations where I am using the main (boot) hard drive and the CD, they each have their own interrupt (this is the common mode when I'm running games). My CD drive is a burner, so I make sure that I burn from an image on the main drive, again so that during the operation I'm always transferring from one IDE chain/IRQ to the other.
I don't know whether any of this matters or not, and I've sometimes wondered if it would be better to put both the hard drives on one IDE and both the slow removables on the other.