yeah, put the 2 hard drives together and the 2 cd/dvd drives together. the primary master should be your C drive and the slave should be the other drive. the cd/dvd drives dont really matter, but if you have a dvd burner, it should be the secondary master.
Each HD should be preferably on a separate IDE, as master.
Thus they can exchange data simultaneously
Then the other elements are slaves.
Of course the boot disk is on the primary IDE
DMA must be selected for the hard drives