notepad can't display an exe file correctly. You need to use a hex editor for that. Also a debugger with integrated disassembler is very useful.
One program that is popular among hackers is hview- It looks like an old dos program but it isn't. It's actually one of the best hex editors/disassemblers around.
If you want to go old school, you can try the prehistoric dos debug program,
en dot wikipedia dot org/wiki/Debug_(command)
It is a very simple program so it might be easier to get into. It's what people in the 80's used to get started with assembler and stuff. But you probably need some kind of dos emulator to run it on a modern pc.
You probably know that in a computer everything is just a sequence of Bits, i.e. 0's and 1's. Code, data, everything. Bits are grouped into Bytes (group of 8 bits).
In a hex editor bytes are displayd as hexadecimal numbers
en dot wikipedia dot org/wiki/Hexadecimal
Every byte in RAM has an address. The first byte has the address 0 the second byte is at address 1 and so on. The processor uses that address to read and write bytes,
Files are also a sequence of bits/bytes of course. So they can easily be loaded into RAM.
EXE files contain the machine code and additionally they got information that windows needs to execute it. Look here
en dot wikipedia dot org/wiki/Portable_Executable