If they're hardcore, anything pretty much before DA is golden. The first set the tone of the series, and the 2nd and Third expanded so much more and included a great multiplayer. The debate will always jump between CT and PT for being the best Multi; but I think that CT ripped it up by far. Less clunky, and it was developed by the Montreal Studio instead of their overseas studio in china i believe it was (and imho, the splinter cell games done by the main branch in Montreal typically made the best polished games compared to their other studios - though the last one was too hollywood-styled; albeit co-op being fun)
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