So you have an IDE drive with Windows XP on it and a SATA drive with FC5? The windows install boots normally but you have to choose to boot from the SATA drive to get linux at all, am I right?
If so, all you need to do is install GRUB in the MBR of the first harddrive (the 'Primary Master'), and add the lines to GRUB's menu.lst. To add those lines to GRUB, copy the contents of the menu.lst out (so you don't mess up booting your FC5 install) and when you need to add your Windows install to the menu.lst, it is something like this:
Code:
title Windows XP
rootnoverify (hd0,0)
chainloader +1
The rootnoverify line is the one that will change. (hd0,0) is the first partition on the first harddisk, (hd2,1) is the first partition on the third harddisk etc.
If this is too confusing, let me know. Good luck!
Edit: pixellany beat me too it, but this is a bit more explicitive so I will leave it here.