I did. I had to reverse engineer a couple of things a long time ago.
To understand how your computer you can write a toy OS (there's a lot of resources to help you). Here's mine: Toy Realmode OS
IMHO, assembly is just a piece of the puzzle, you gotta understand how things work together. Some questions I had out of sheer curiosity in the past:
.elf or .exe file?for loop is implemented in the binary file, what sort of op codes the compiler use, how will it optmize the code? (Programs written in C)If you want to take a look how everything fits together I recommend this book, it will teach you lots of interesting stuff.