This is a bit trickier than it sounds. Are the drives jumper'd as Master and Slave or are they Cable Select (I'm assuming that they're IDE drives)?
Depending on how the drives are jumper'd (and if the boot sector of the drive with the legal copy is intact), you may be able to just remove the drive with the illegal copy and boot from the drive with the legal copy on it. Otherwise you'll have to jumper that drive as Master (also, for computability you may want to connect it to the far end of the cable - leaving the middle connector for the other drive). Also, you may have to go into Disk Management to assign it to the C: drive.
Once that's done, jumper the drive with the illegal copy to Slave and plug it into the middle connector on the cable. If all goes well, you should be able to see the drive in Windows.
A couple of warnings here;
1) Ensure that the system is unplugged from the wall and that you're touching the metal of the case whenever your hands are inside it. Static electricity can fry the hard drives.
2) You may have problems accessing the data on the other Windows installation (Access Denied errors). To fix these, just take ownership of the files while using the legal copy of XP. Here's some more information on this issue: http://www.bleepingcomputer.com/forums/t/42756/how-to-fix-an-access-denied-errors/
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