In the main game - before you beat the Elite 4 - you can only catch the new Unova pokemon in the wild.
After you obtain the National Dex, you gain access to the PokeTransfer in which you can transfer Pokemon from other regions. You need two DSes for this, as opposed to in D/P/Pt where you used GBA+DS slots.
Also after you get the National Dex various older Pokemon are catchable in the wild. But many are not - see here for the list of unobtainable pokemon: http://serebii.net/blackwhite/unobtainable.shtml
Like that page says, many of them may be available through the Dream World at some point. It depends what Nintendo/GameFreak decide to put on there.