Well, I have 100 in small guns. Is there any point in increasing past 100, or can I move on to, say, barter or science?
Yes, you should take it up past 100. Allow me to explain
The combat system in the original Fallout games actually played out very well on paper, (so much so, that if you were a particularly adventurous D&D style gamer you could play it as a pen and paper game and even print your character sheets right out of the game). The game essentially determined whether or not you were going to hit someone (and what your chances of hitting them were) much the same way a human Game Master would in a pen and paper session; it would take your base skill for the type of attack you were using, then subtract your opponents current armor class, deduct perception penalties if necessary, and deduct any range penalties that may apply to the type of weapon your using (IE hunting rifle at close range/shotgun at long range). The end result is your chance to hit, with further penalties for aimed shots (head, eyes, etc) And you always have a 5% chance to miss.
So lets say you have 100% in the small guns skill, your target is at very long range for your weapon and perception (about a -10% chance to hit), your enemy has an armour class of 20, and an additional 3 armour class from extra action points from his last turn. That translates into 100 - 10 - 20 - 3 You chance just to hit your target is 67% - 5% (that constant 5% chance you'll miss). Say you're making an aimed shot for the eyes, that's another -20% so 42% chance to hit.
If you were dicing it up you'd essentially roll two D10 dice, any result 42% and under means you hit your target, any result over means you miss, a 00 means you critically miss and something bad happens to you (gun blows up in your face, lose your ammo, if you're name is Vic you somehow manage to cripple both your legs)
Bump your skill up to 170 and you're looking at 170 - 10 - 20 - 3 = 147% - 20% for your aimed shot to the eyes = 127% which really comes out to 100% and then deduct your 5% chance to miss and voila, you have a 95% chance to shoot his eye out.
(While aiming for the eyes is a good way to score crits often, if you're not one shot killing with eye shots I always found it better to aim for the head. Easier to hit and carries the chance of knocking the opponent out and removing them from combat for a few rounds while you deal with their friends)
Hope that clears things up for ya.