I understand what the two are used for, except I don't know what each does--i.e. what one is for vs. what the other is for. (I usually set them to the same account anyway.)
If you're not sure what accounts I'm talking about, in the IIS manager thingy:
That is the account under which the worker process will run when anonymous access and impersonation both are enabled. If you have impersonation disabled it will run under the default app pool account. Check this for more info.