To simplify what Ross said:
If you look on the back of each of the drives, you'll notice a small group of pins (usually between the IDE connector and the power connector), 2 of which will be connected (top to bottom) with a jumper.
There should be a diagram on the top of the drive which tells you what the jumper settings should be (beware though, they differ from drive to drive - just to make things complicated).
If your CD-ROM and CD-RW are both connected to the same IDE connector, you need to make sure that one of the drives is set as the master and one of them is set as the slave. If they're both set as master, only one of them will work.
To change one of the drives to slave, all you need to do is move the jumper to the right pair of pins, as per the diagram on the top of that drive.
Hope this helps
Rgds
AndyF