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I think ubuntu is a good place to start with Linux as it is so user friendly. You will have no troubles installing it - click click click - done. None of this waiting for Windows rubbish... you should be finished in about 30 minutes.
I think you'll be able to make a decent set up on your old PC for the cost of a blank CD. (Or if you are really strapped for cash you could borrow a large USB stick and boot the live CD from there - or even do an internet install - oh my God you windows users haven't a clue what can actually be done with a computer!)
Once you've got Ubuntu installed I then recommend you start messing about with different Linux distributions by installing them in virtual machines.
Learn the difference between Debian and Red hat based distributions.
Good luck
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