I've only tried PES 2011 and FIFA 2011 on PS2, so I can't really tell about the PC version, but from my experience in both games I got addicted to PES and eventually threw away FIFA xD...
But in PC I believe FIFA is better, I've only tried FIFA 2008 as my PC can't handle higher graphics, and it has more control and more options in my opinion, and it's more realistic when it comes to the moves, and not the graphics.
If you're asking to know which one to play as for the 2013 versions, I recommend FIFA.Scratch that, I just played both games PES 2012 and FIFA 2012, PES was more appealing to be honest
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