Guybrush's hand gets immediately and fully infected because it's touching LeChuck when he's stabbed; if you notice, LeChuck is actually holding it.
The pox appears on people when negative feelings boil to the surface - anger, for example. I think of it as a physical representation of the "Mr.Hyde" aspect of a person: if a person gets angry, it will appear on their skin; it's important to recognize that this anger only taps into feelings that are already there. The pox doesn't make them angry; they get angry, and the pox just increases it, gives them red eyes, green skin and makes them shout.
The other pirates get infected quicker because they get angrier quicker.
As to why LeChuck isn't infected: I'm not sure, but I think it may explained in two ways.
1. It's his own pox. He may actually be immune to it.
2. Notice how completely calm he is as a human? He may be infected, but since he's never angry, the pox hasn't shown up on his face and hands. It may have been on his body, but we never see that. Or it may have been inside him, but without a physical representation at all.
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