My favourite (perk) is probably Boone's Spotter, it's invaluable and makes long-distance sniping much much easier, especially at night. Veronica's Scribe Assistant is pretty useful too, especially as an energy weapons user (recycling ammo). I've heard many people recommend Whiskey Rose, but since I rarely consume alcohol anyway (unless I'm at the end of a killing spree and need to bump up my carry weight a little) I haven't gotten much mileage out of her perk.