If you connect the 'guest' hdd to to a hdd connector and it gives you a master/slave problem, you can temporarily disconnect your dvd-rom and connect the 'guest' hdd instead. This needs one restart and is sure to work with the IDE connectors. The 'guest' hdd is automatically detected.
Depends on what content you are wanting to move. If you are trying to move an installed OS you will need to use a software solution, personally I prefer to reinstall and start over fresh, but there are several options out there acronis is one and WD used to have a free one you could download.
Now if you are just trying to move some data files. You simply install both drives and then cut and paste away.
If you want to simply copy some files, yeah just plug them in, copy and paste, nothing to it.
If you are talking about moving your OS, applications, everything to another drive, then you must use a software solution capable of "mirroring" your drive to another drive. Acronis True Image is one, there is a 30 day free trial download, and it works great, step by step instructions, very easy program to use.
If you are talking about using more than 1 drive at the same time like 1 larger drive for speed or storage, then you want to look into what is called RAID. There is a whole world of information you must sift through about RAID though, and Google is your friend to find it.
If you want to connect two drives into your Computer and use them both at the same time, you just plug both cables direct to your motherboard and to your hard drives and Windows will recognize them.But make sure the both hard disk you are connecting is not SATA hard disk. Sata drives don't have jumpers for connecting two drives, but they do have jumpers for Transfer speed which you do not need to touch.