is it possible to view behind the scenes of an exe file once its executed?
Technically, yes. Practically, no.
While it is possible to open an exe file with an editor and inspect its contents, like you do for a website with F12 in the browser, a really big difference between an exe file and a website is that the code of the website is distributed in the form of more or less human-readable text which gets interpreted by the browser. An exe file on the other hand is in a binary format that can be executed almost directly by the processor. Those instructions are essentially unreadable for humans.