I'll list the best perks in a orderly fashion but they aren't in order in which they are obtained; then i'll list the few skills which are important while others are just obsolete.
#1 Pack rat - no question about this is the #1 perk there is in this game, at least if you play on hardcoe.
#1 Educated - tied for first place with pack rat
#2 Better Criticals - this perk + a sniper rifle + sneak attack is almost a guarantee one shot one kill, even if your getting critical hits which aren't sneak this perk is in effect.
#3 Jury Rigging - repairing guns that cost 4,000 - 7,000 caps to buy with guns that are bought for 75-200 caps is just plain outright cheating, cheating in a form of a perk.
#4 Finese - self explanatory
#5 Sniper - all you will be doing in this game is aiming for the head
#6 Action boy x 2
#6 Grim Reaper sprint
#7 Strong back - 50 extra pounds worth of pack rat ammo weight, yes pls.
#8 Chemist - double duration on bullet time. And your jet/psycho last forever even while fast traveling throughout the tiny map New Vegas has to offer.
#9 Silent running
Debatable perks
Comprehension - I picked this up before reading any skill books, have to say i maybe came across a few with the whole map explored possibly the only perk i regret picking up on my lvl capped toon, probably would of grabbed a S.P.E.C.I.A.L. increase at the level of this perk, the choice variety when i picked this up was very small.
Concentrated fire - I believe enemy needs to survive the first bullet from the anti-matter rifle for this perk to have any effect. (I didn't get this perk)
Hand Loaded - There is ONE good schematic which is for the .308 (sniper rifle ammo) which increases the damage by 50%, the problem is once you reach end game, w.o doing the main questline so you can free roam, the sniper rifle gets replaced by anti matter rifle and last i remember hand loaded doesn't offer any .50 schematics. (I didn't get this perk)
Math wrath - grabbed it @ lvl 30, nothing else that was good at that point, this perk is weaker than action boy but becomes appealing after you've selected from the only decent dozen perks there are.
The most optimum way to characterize your toon's special at creation screen is the following.
Str - 5
Per - 6
End - 9 (for all implants)
Char - 1
Int - 9 (for max skill points)
Agi - 6 (with small frame)
Luck - 5
You may tweak a point here or there depending which trait you go with, small frame or four eyes or both. You'll also want to get a intelligence implant as soon as you get the caps for it to increase it to 10 which will further provide more skill points.
Skills you'll want to max but not to 100, until you start coming close to lvl cap, you'd want to leave them at 88ish in case you come across 3 books that increase your repair skill, and with comprehension thats +12 points. So you don't want to have 100 skill cap before your 30, otherwise skill books go to waste.
Most important 3, want to use all your skill points from the beginning to increase these 3 skills to 70-80 range.
Guns
Repair - Jury Rigging requires 90, and even if there was no perk as such, you'd want to increase your repair really high.
Barter - Not only is this perk offer you dialog on almost every quest to increase your reward, but its a pre-req for pack rat, the best perk in the game.
Science & lockpicking, . Fun fact from my lvl 30 general statistics page: You've hacked 10 computers, you've picked 104 locks. Just from that statistic you'd think lock picking is superior but science is used for some dialog and for crafting. I ended up at 80 science 55 lockpicking when i hit cap, and w. a magazine used, that becomes 100 science & 75 lock picking.
Sneaking - ended up at 92.
Bad skills
Speech
survival - collected raw meat from a pack of bullhorns will last me for 5 years on hardcoe mode, why look any further into this skill and the useless campfire crafting thats associated w. it.
Energy weapons - Guns are 100x more superior
Explosives - Energy weapons are 100x more superior, i guess this makes guns 10,000 more superior then explosives.
I left out all the melee related talents & skills as it is a completely inferior game play vs a character that goes guns. But nevertheless can't compare the 2.