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If you really want to get a solid, extensive experience, start with Platinum. Follow it up with Heart Gold or Soul Silver, then Black or White, then Black 2 or White 2, and then X or Y, and Omega Ruby or Alpha Sapphire. Between these, you'll get to experience all of the regions (although you won't get to experience Kanto in its original storyline - I suspect a chance to do so will occur soon enough, anyway).

Why? Because this sequence lets you experience all of the regions, and builds up in terms of complexity without any major gameplay changes that could easily throw you (Gen III, with Ruby/Sapphire/Emerald/FireRed/LeafGreen was before the big physical/special split, and a number of other features that significantly change the gameplay weren't yet present either). Anybody who has played Gen V will feel odd playing Gen IV because of what changed between them, and same for Gen VI and Gen V. Once you've played X/Y/OR/AS, specifically, playing B/W/B2/W2 will feel really odd, because the shift from sprites to 3D models has a huge impact on the feel of the game... but progressing forwards through them won't feel odd because each generation improves on the previous ones in terms of graphics.

If you just want to experience modern Pokemon, and are happy to build forwards only, with the one-to-two year gap between games, then I'd suggest starting with X or Y. Everything before that is redundant if you're not concerned about experiencing the various regions, etc. Follow it up with ORAS.

There's no real reason to choose any other path than one of the two I've established above. You could, for instance, go all the way back to the start, with Red/Blue... but while they were amazing games for the time, they're just not up to scratch nowadays (primarily due to issues that the first two generations had, that were fixed in the move to Gen III), and even if you want to experience Kanto "properly", you're better off going with Fire Red or Leaf Green... and as I said, it'll get another remake soon enough.

If you really do want to experience Kanto properly, and want to start with Gen III... then I'd suggest skipping Ruby/Sapphire and going to Emerald... and also playing Colosseum and XD, as they're certainly unique experiences relative to the other games, and if you're going to insist on experiencing it all, you might as well include them, too. But I'd say starting at Platinum or X/Y is best.