Catcher: EPO, or very rarely DEX
Juniper: BWI or DEX
N: NVI or DEX
Cheren: EPO or DEX
Bianca: EPO
DCE: NXD
Level Ball: NXD
Ultra Ball: DEX
Eviolite: NVI
Heavy Ball: NXD
Rare Candy: DEX
Dark Patch: DEX
Tool Scrapper: DRX
...these are some of the staples you'll need for a lot of decks; concentrate on buying, like, four packs at a time to collect staples from whichever sets you imagine you'll need. Once you've got all the staples you're interested in, take a look at what Pokes you've pulled, and pick a deck to try for. Then go heavy into that set.
For the record, I've bought a couple hundred packs, and my distribution is (guessing):
BW: Not many
EPO:a painful 10% just to get 3 Catchers
NVI: 5%
NXD: 10%
DEX: 50%
DRX: 25%
...but I picked up a bunch of staples from theme deck code cards, too.