You should try PsxMC. It's better than Psmplay, IMO. Anyway, if you still want to use it, just right-click anywhere in PSmplay and go to Options -> Assign CDROM drive. There you can select the drive you want to use.
That's what I thought, Zephon. Unfortunately. mine doesn't see any of my drives. Went throught it with my bro & he's confused as I sent him the same zip file. Works all fine & well for him but mine's messed up. Maybe it's a problem from my bnurner runnig in the background? Don't trouble yourself anymore about it though. Thanks for all the help guys.