Check this out.
A while ago when I was interested in RE someone suggested I learn C and x86 ASM first.
I managed to go through one C book before I realized it wasn't my thing.
As far as I see it, ASM/RE aren't difficult. Just plain boring and tedious.
You need a special mindset to become any good so to "edit and make my customs to .exe compiled files" you will need to spend several years studying the boring stuff first...
Read About DOS 16 Bit Edition(the 32 bit edition speaks of HLA), but to start learning assembly you must have basic understanding of one of the high level programming languages, and always read about C and windows API(or C API's).
When the language is as specific as Assembly, the code would be so complex, chances are you wouldn't even be able to find what you're trying to change in the first place.