Vash uses his childish personality to mask the fact that he is a suffering man. He wants the world to be a better place, but knows that outlaws and Knives are making it a terrible place to live. He is hopeful and optimistic, can be cold at times; but aims to be a child at heart to both protect those around him and to make others not suspect about his bounty. He hates the idea of killing to such a degree that he downrights refuses to kill.
Deadpool on the otherhand is childish to both spite his enemies and humiliate them with sarcasm. He likes killing and has only once followed a moral code, and that was when he covered for spider man for a while that Peter was sick.