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Technically it isn't really a process anymore, just a listing of one. In order to get rid of a defunct or zombie process you'll have to kill it's host process.
You can find that out by using the command ps axjf. Once you find the host process just type kill -9 <process number>
If there is no host process you'll either have to reboot the system or wait for the system to clean it up, however a few zombie processes generally aren't anything to worry about as they aren't taking up resources.
I dont' know a whole lot about this stuff, but you might try running XMMS from the commandline exclusively for a bit. Tedious, yes, but when something goes wrong you can see any errors right there in front of you. I had trouble with this before, and I can't remember exactly, but I think at least when I ran it from the commandline if I had to Ctrl-C it, I didn't have to wait for the defunct process to clean itself up.
Might also check ~/.xsession-errors after it crashes, if you didn't run it from the commandline, and see if there's any info there.