Well, PVD has such a wide array of tracks, some being not so stellar as others, that it would be wise to make a proper selection.
I'm unfamiliar with some of PVD's earliest offerings, which are very much touted as being some of his best work, so I can't help you there. But I'm sure someone more experienced with PVD's early days can help you out.
As for PVD's "best track" I would say definitely go for For An Angel (IMHO). Personally I like PVD's E-werk Club Mix the most, for it retains the charm of the original as well as injecting some energy to make it dancefloor-friendly.
Some other PVD tracks that I think would make a good choice include Another Way, Tell Me Why, Out There and Back and others.
As for remixes, two really stand out for me:
Romanthony - Never Fuck (PVD's Late Night Remix), and
The Space Brothers - Everywhere I Go (PVD Remix)
I really think these two hit the spot. Some people don't like the Romanthony track, though, so I guess it's a hit-or-miss matter based on your personal tastes.
On top of that I would suggest that you go out and get some of his albums. Two noteworthy ones are Out There And Back (also the name of one of his tracks) as well as the Politics of Dancing 2-CD set.
Especially the latter - I *definitely* believe this would be a great introduction to PVD in general. This is because PVD isn't only about the tracks he produces, but ALSO about the music he plays. It would do your friend good if he heard not only some of PVD's own music, but also PVD at work spinning one of his awesome sets. In that regard you might want to download some of PVD's live sets as well. The cheering and enthusiasm of the crowd will impress your friend I think. You have a decent selection here on TA itself. I recommend the Mayday 2000 or Live @ Home 2000 live sets (especially the latter).
Hope that helps! 
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