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On Windows hold shift then press the media keys to control a second (background) program. Found this out purely by accident in this exact scenario, VLC in foreground and Spotify in background!!!

Ah interesting question.

This thread implies that there can be a war between apps fighting for control

https://community.spotify.com/t5/Desktop-Windows/Media-keys-....

I've never really used the media keys, so have no idea how it really works in practice. Might have a play when I get home later.

On Windows VLC will swallow hot keys if it's on top, otherwise they are caught by spotify. If they are both in the background it's spotify. If there's another app that listens to the same hot keys, I think (pretty confident) that it's the last one to register for the hot key.

As other replies pointed out, this is handled by the OS. Seems to work well most of the time for me on Ubuntu.

I think the media key interuption dispatching is handled by the OS and not the apps