If you can only get one episode, I'd recommend Reality 2.0. Chariots of the Dogs and What's New Beelzebub are both great episodes, but they're better once you've played the other episodes in season two first.
Chariots of the Dogs and What's New, Beelzebub? are my favourite episodes.
But like Jake said, they're much better if you've played the rest of the season already, so you should get Reality 2.0. It makes more sense when you don't know who these characters are.
That's a hard choice since they are both three amazing episodes. As Jake and Shwoo say above, I'd go with Reality 2.0 (although starting from the season beginning with Culture Shock would be better), and then buy the later episodes when you can.
I recommend you play them like how you would watch a TV series: Not Random. So I agree with everyone else so far (or jusy go for Culture Shock if you REALLY want to play it like a TV series).
Culture Shock, and Ice Station Santa don't have anything to do with the storyline, you should get every Episode after that, but it's good to get the first Episodes, cause they're fun, and some things actually come out in other Episodes after that one.
I would also get Reality 2.0 if its a choice between that and the second season episodes. The individual series 1 episodes can be played with less confusion than series 2, which is more linked.
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But like Jake said, they're much better if you've played the rest of the season already, so you should get Reality 2.0. It makes more sense when you don't know who these characters are.