I've been contemplating this for a bit now. I can't settle on whether to start with Snivy or Oshawott because I have two builds in mind:
Mareep, Pidove, Sewaddle, Oshawott, and Riolu.
or
Mareep, Pidove, Snivy, Psyduck, and Riolu.
Suggestions?
Between the two, the one with Sewaddle and Oshawott is definitely better. Both of their final evolutions (Leavanny and Samurott) are better than the final evolutions of the other two (Serperior and Golduck).
I've tried a build with Tepig but he's too strong for his own good. He kills anything I have my eye on to catch! I suppose if I had to settle for two I'd pick Riolu and Oshawott. (Even though I'm tempted to pick Pidove, Flying is amazing.)
If you're trying to catch something, a good strategy is to switch in the weakest pokemon you can get away with (weak enough that it's not likely to faint the other pokemon but not so weak that it gets fainted itself), then use a weak, and if necessary Not Very Effective move against the pokemon you're trying to catch. Just keep chipping it down slowly until it's low enough to catch.
And Leavanny (and some other pokemon) can learn a move called False Swipe that always leaves a pokemon with 1HP, so it's impossible to faint them. That's the best catching move.
It can be a bit complicated to get that move on Leavanny though. In Black and White, you get a TM for it fairly early - once you've seen 25 pokemon, just report to Professor Juniper and she'll give it to you. But in B2/W2, the TM is in Reversal Mountain, and you can't get it until very late in the game. Leavanny can learn the move naturally though... sort of. It's a move that it gains access to when it evolves from Swadloon to Leavanny, but it's technically a Level 1 move (a fair number of final evolutions get moves like that). Since it didn't have access to the move when it was a Level 1 Sewaddle, it never learned it, but since it has access to it as a Leavanny, it can "relearn" it. To do that, find the Move Reminder (in B/W, it's in a house in Mistralton and in B2/W2 it's in a booth outside the Pokemon World Tournament in Driftveil). In exchange for a Heart Scale, the Move Reminder can teach the move to Leavanny.