Personally I would start with X/Y or ORAS, because those are the more recent ones and both are IMO, pretty good.
After that, you can choose weather you want to get earlier games. If you want to try out B2W2, try out Black and White first due to references and story. (B2W2 is regarded to have the best story in the series)
Other than that, you can choose Platinum and etc before the first installments (Diamond and Pearl) and etc.
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