My tips:
- Science and lockpick are important for all characters
- Collect every bit of rubbish early on and sell it.
- Don't follow the main quest too closely, there's plenty to do and it can wait.
- Speak to everyone and take notice.
- Really explore Megaton and it's immediate surroundings.
- Load up all the GOTY extras right away but don't play them for a while.
- Get the Ghoul mask as soon as possible.
- Save frequently (and as you leave the vault)
- Oh and there's a lot of useful stuff to be picked up in the vault before you leave.
These are pretty good tips, the ones I would add are:
BEST TIP
Get 9 Intelligence when doing Special, then, go to Rivet City right out of the vault and go the Science Lab and get the Intelligence bobblehead. At level four, get the Educated Perk. This will give you a ton of skill point and you will have 100 in all the essentials by the time you get to higher levels. Trust me, this will make a huge difference.
-Try to only specialize in one type of gun set at first. (Big Guns, Small Guns, Energy Weapons, Melee) I would not recommend unarmed. The key is to not try to be the Jack of all trades, it's not Oblivion. You can't do everything, so pick a style and stick with it. It's a lot more effective to be great at one thing than okay at everything,
-Grab the medicine bobblehead in your father's office before taking the G.O.A.T.
-Putting points in Barter and Speech gain save you a loooooot of money.
-If you pick Energy Weapons, do Mothership Zeta first, if you pick small guns, do Point Lookout, if Melee, do the Pitt
-Once you play The Pitt, do the Steel Ingots quest, you will get some great armor and one of the best guns in the game, especially for stealth
-As far as Perks, get Strong Back and Scrounger. They will help a lot.
-Go to Springdale once you leave the vault and find the only shack you can go into, and kill the girl for a quick 400 caps.