For Bond, anti-addiction stuff because you better be drinking 24/7. Get Cass with you for Whiskey Rose, and get plenty of Sneak and related perks, especially ones for criticals. Go for headshots, and no Mysterious Stranger because that's your job. The light/no armor perks, since you should be wearing a tuxedo as much as possible. Also, Sean Connery for your character's looks.
For Ash, Wild Wasteland is mandatory, as is Bloody Mess, and Hand Loader, Mad Bomber, and Jury Rigging. Don't forget Explosives, and keep plenty of Powder Charges handy.
As to my own silly idea, Sterling Archer. 1 INT, high Luck, End, and Cha, insult everyone you see and resolve things as violently as you can even when they've somehow already been resolved peacefully, and take over Vegas for yourself.