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https://steamcommunity.com/groups/bigpicture/discussions/
1. Switch to another screen (duplicate/extend/only 2nd screen, I do recommend only using 2nd screen because some games wont scale properly)
2. Switch to another audio output.
3. Launch steam in big picture mode
4. Switch back to PC screen
You'll need AutoHotkey and a program called NirCmd which allows you to switch audio output with a command line.
My AHK script:
Numpad1::
Run C:\windows\System32\DisplaySwitch.exe /external
Sleep 2000
Run C:\windows\nircmd setdefaultsounddevice "TV" 1
Run C:\Program Files (x86)\Steam\steam.exe -start steam://open/bigpicture
Return
Numpad5::
Run C:\windows\System32\DisplaySwitch.exe /internal
Sleep 2000
Run C:\windows\nircmd setdefaultsounddevice "Headphones" 1
Return
I hope this helps!
note: I also tried using the "Preferred Display" option in steam big picture. But it doesn't seem to work for me.