Simple enough, I would probably just put the two hard drives on one channel. If your motherboard supports ATA66/100/133, use an 80 wire ATA cable and set both hard drives to cable select. Whatever drive you want to have as your C:\ drive, place it at the end of the cable. The second drive will be in the middle position, and the blue connector will go to the motherboard. As for the DVD and CDRW (I'm assuming that's what you meant and that you didn't need a CD-Rom in there as well as it's kinda pointless), it really doesn't matter which is the master and which is the slave, but you have to have one of each, you can't have both as masters or both as slaves.
-At Ford, quality is job #1, job #2 is making them explode. ~Norm MacDonald, SNL News
-Switching to Glide..Balancing in my head..inside of me...
taking the glide path instead.