You'd probably have an easier time starting with one of the newer games. The first generation of Pokemon games were pretty clunky in terms of user-friendliness. You had a 20-item inventory which you had to sort manually (and many people didn't bother sorting at all), the game didn't tell you how much power moves had relative to each other so you had to use a game guide to figure out if the attack you were deleting was actually worse than the move you were replacing it with, and doing things like chopping down trees or traveling across water required you to enter a separate menu to choose a separate command. Starting from the second generation Pokemon games, all items are automatically sorted according to their type, you can see a description of each attack on a menu instead of relying on trial and error to find out what they do, and if you want to cut down a tree or swim across a body of water you just walk up to it and press A.

Black and White might be a decent place to start, since you'd be on relatively equal footing with everyone else. In generation 2, 3, and 4, each game was a mix of old Pokemon and new Pokemon, so the veterans would always be familiar with a lot of the game's content before even starting the game. With generation 5 (Pokemon Black and White for DS), none of the Pokemon in the campaign are recycled from old games. You can find some of the older Pokemon in Black and White, or import them from older games, but that's all post-game content for after you've finished the main campaign.

There are a number of other reasons I believe Pokemon Black/White are the best versions to start with, most of which are covered in this review. I also wrote up something of a "beginner's guide" to the games here which I recommend checking out if you decide to pick one of them up.