i'm always evil, i can't help it honestly.
just because you're evil, doesn't mean that EVERYTHING you do is evil.
you should treat all opportunity's as tho you were good. act as tho you're friendly and willing to help, leaving npcs vulnerable or unaware to your true plans.
when the opportunity arises do what you want. be it rob them as they sleep or put a bullet in their dome for lols (grenade in the pants is always fun, too). just always make sure you walk away with something (ie quest reward, more caps, items)
-protip: if your planning on being evil for no reason you might as well be shooting yourself in the foot.
There are different kinds of evil.
There is the psychopath evil for example. who would have no problem cutting a baby in half and throw one half to his mother just because he feels joy from others suffering.
There is the selfish evil. He does not always resort to violence unless there is some kind of self-interest for him. He is just cruel. Instead of killing the baby, he would kidnap the baby and turn him into a serial killer.
Then there is the evil person with a code. He follows it strictly. For example he kills people for his God (like the crusader) But he would never nuke Megaton.
from http://www.bbc.co.uk/dna/h2g2/A2309230
Here are the nine D&D alignments and what they mean:
* Lawful Good (Crusader) - Loyal, hard-working members of the community, or truthful and honourable fighters against evil who hate to see bad go unpunished. They believe that having an ordered society is the best way to further the common good. Example: King Arthur.
* Neutral Good (Benefactor) - They believe that a balance somewhere between total order and total chaos is best, and would generally concentrate on doing the morally right thing without worrying about whether it was good or bad for 'society'. Example: Mother Theresa.
* Chaotic Good (Rebel) - Strong believers in freedom who like to make their own way and hate people who bully other people and try to push them around. They will often have a strong moral code which may not agree with the law. Example: Robin Hood.
* Lawful Neutral (Judge) - They are disciplined and believe that adhering to and enforcing laws and traditions is the most important thing. They will not generally go out of their way to help others but will intervene to stop crime. Example: Asimovian robots.
* True Neutral (Undecided or Balanced) - This can mean either of two things, depending on whether the character is actively or passively neutral. Active neutrals (the Balanced type) are very rare. They are philosophically committed to maintaining the Balance, and will tend to join every fight on the losing side. Passive neutrals (the Undecided type) are somewhere in the middle on both the Good-Evil and Law-Chaos axes. The passive neutral alignment can also apply to creatures with no moral sense such as animals. Example: Zen masters (Balanced), animals (Undecided).
* Chaotic Neutral (Free Spirit) - A strange and very rare alignment. Chaotic neutral characters are very unpredictable individualists, being governed by whatever they feel like doing at the moment. Example: Calvin (from Calvin and Hobbes).
* Lawful Evil (Dominator) - They respect the law, but have no concern for others, and tend to exploit the law to rise to power. Often they will engage in merciless, organised, planned killing. Example: Adolf Hitler.
* Neutral Evil (Malefactor) - A purely selfish type, with no concern for other people or the law, but without as much lust for killing as Chaotic Evil characters. Example: Case (from Neuromancer by William Gibson).
* Chaotic Evil (Destroyer) - The most dangerous characters of all, they will rove around killing and destroying for the sheer joy of it. Example: orcs.
If all that was too long and confusing, D&D Adventures has a short explanation of each alignment in terms of 'I'll kill you because...' If you are playing a pacifist character, or just trying to determine your real-life alignment as an ordinary person who has never killed anyone, you might prefer the descriptions below in terms of 'I'll heal you because...'
* Lawful Good - society is better off when people help each other.
* Neutral Good - you need it.
* Chaotic Good - I want to get back at the uncaring society that left you to die.
* Lawful Neutral - the law obliges me to.
* True Neutral - you'd do the same for me (for the Undecided true neutrals, by anology with them killing in self-defence at the website above) or you are the underdog (for the Balanced true neutrals who join every fight on the losing side).
* Chaotic Neutral - I feel like it.
* Lawful Evil - you are vital to my conquest of the world.
* Neutral Evil - there's a nice reward for it.
* Chaotic Evil - I want to torture you more before you die.