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HG/SS's enjoyment comes greatly from the nostalgia, but still, they are pretty solid games that you can start on.
Black2/White2 are arguably the best in the series yet, great graphics, battle style, mechanics, available pokemon, postgame, etc. You don't really need to play the first installment of these versions, but it does add a little to the story if you chose to.
However, if you start with these, it's going to be hell to go back and play the others, so it comes down to preference. Starting with the first pokemon game ever, or the best in the series.
