Each different type of birth control has a different percentage rate of working, and if you take them correctly, then they should be at those numbers correctly. I'm very fertile, and have been on both the Pill and Mini Pill and haven't gotten pregnant, yet every time we try I get pregnant that month. I'd suggest talking to your dr and they can suggest one that is best for you.
The morning after pill is the only one I've heard of that can help after the fact.
No form of birth control is NOT 100% effective, but it does lessen the chance of pregnancy. Plan B is also not 100% effective, like alaysha said, but if the egg has already been fertilized it will not abort the pregnancy.
Of course part from the morning after pill as alaysha says.
Contraception is used to prevent pregnancy,You use this before having sex.
Of course birth control works that is what it is designed to do. As for working after you already had sex. Probably not since it takes at least a week to kick in. But the morning after pill (Plan B) is like 85% effective. It doesn't completely get rid of your chances of getting pregnant but it does severely limit them.