Most here would agree that PES or WE are both better (more playable and compelling) than FIFA.
Most people will be using a PS2, some modified with chips to play imported or patched versions of the game.
e.g. WE7 is a Japanese/N. American import.
There is some growth among the PC playing contingent, but you'll have more options open to you using a PS2: option files can be exchanged over the interet using an X-port, and most 'patches' (i.e. modifications to the original games PES3 and WE7) will be for the PS2. See the Editing News on PESInsight's homepage, or the Editing/Patching forum here to see what's possible.
The BIG difference between FIFA and PES/WE to my mind is...
FIFA seems to be mostly about learning set moves that will always work in all situations. EA's tendency to offer 'special moves' makes the game like a Street Fighter-type game played on a football pitch. If your opponent knows more of those special moves than you do, you're sunk.
I left that series behind in disgust around the time of FIFA2000, that was when they introduced some spinning turn that left glitter sparkling your player's wake - and I could not accept that at all. No way, never.
I'd more of less conquered it anyway in a matter of days, and with no more to learn there wasn't much point in playing. £29.99, I still feel cheated!
Maybe FIFA have improved since, but I couldn't be bothered looking.
By contrast, in ordinary gameplay PES/WE relies on much simpler controls, and rewards all the things sideline coaches shout about - screening, sharp passing, making an extra man in midfield.
These simple moves seem much more subtle and variable than FIFA's. You can't just press a set sequence and have your players ping the ball about like a they were in a set dance going up the field - you have to work to win space and guide your passing and shots.
Although FIFA may shift more units, compare the devotion of each set of fans. Take a peek here:
http://www.soccergaming.tv/forumdisplay.php?forumid=59
I only bought my PS2 to play one game, PES2. And PES3 is a vast improvement.
The only caveat would be to say many who've played both PES3 and WE7, a lot prefer WE7. That would require either a 'chipped' PS2 to play on import, or a Non-European PS2 which you can purchase on-line.
I'd start with PS2, playing PES3, then consider an X-port which will allow you to take advantage of Option Files where people have updated and corrected team line-ups, kits etc.