Look up the bobblehead locations on the net (easy to find) there's one for each skill (+10 to that skill) and one for each SPECIAL stat (+1 to each).
The best weapons in the game by far (stat wise, assuming you've increased small guns) are:
Xuanlong rifle (chinese assault rifle)
Lincolns repeater(hunting rifle that is 100% accurate and fires .44 rounds)
The Terrible shotgun(combat shotgun)
Ol'Painless(hunting rifle)
They are all better than the guns that can be used to repair them, by quite a large margin. Making a sneaking headshot with the lincoln repeater will fell almost any enemy, even deathclaws will be almost dead if you pull it off, although they are hard to sneak up on. Infact sneaking attacks in general are just a good idea because you get an automatic critical hit, which means you kill them faster and save bullets.
Nuka-grenades are devestating, much more so than frag grenades.
Killing deathclaws can be killed VERY easily by employing the dart gun. It will cripple their legs meaning that there is no way they can catch you. It's literally like shooting fish in a barrel!
You can easily raise every skill to 100, especially if you collect the bobble heads and make sure your intelligence starts high and that you collect the intellgence bobblehead from rivet city early on. (unless you have the broken steel add-on, if you leave the bobble heads until you become level 30 you can actually get 10 for every SPECIAL stat if you choose the almost perfect perk when you reach 30. This is more a matter of personal preference than whats best)
If you're planning on doing a lot of exploring then take the education perk - this means each skill book raises your skill by two as opposed to just one. You'll be surpised just how many skill books are out there if you look!
And finally....don't fire the MIRV underground. Unless you want to see your character get vaporised
