If you would like to gain a more technical insight to the PE format then read Matt Pietrik's article in MSDN titled:

"Peering Inside the PE: A Tour of the Win32 Portable Executable File Format"

It even includes the source in C to a utility that enables you to dump all manner of PE files. I think theirs even a supplementary article that will allow you to gain access to parameters etc by decoding any available debug information.

Its complex, but a great insight into these things.

PS As Ed Rauh (before he shouts at me :-)) rightly points out the API docs are a better place to get this type of information.