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2. It depends based on what you are doing but essentially it will be your 'select' button in games. (as in game controllers with select and start) In other apps it does other stuff but not always
3. If you are using the desktop mode then Steam has to be open (can be minimized) in order for most of the controls to work. Big Picture mode has more settings that you can set to your liking for using the steam deck in desktop mode.
For example if the left analog click is run I change it to a back button so the analog doesn’t get beat to death.
https://www.steamdeck.com/en/tech
In some other controllers the button between d-pad and left stick is known as "Select" button and the one on the right side between ABXY and right stick is known as "Start" button.
As for R4/L4/R5/L5, those most likely don't have default actions in the desktop mode and have to be configured separately.
Thanks, T
Basically, if you want to use a gamepad you're stuck with game mode and if you want to use a keyboard and mouse you're (mostly) stuck with desktop mode.
I know this because, wen I configure DuckStation in Gaming mode, pressing on left of d-pad or left of left trackpad assigns the same input.
Valve being Valve, instead of cutting down trees to help you get acquainted with your Steam Deck, they instead created a small (free) game:
https://store.steampowered.com/app/1902490/Aperture_Desk_Job/
Desktop mode has a desktop configuration that is used. Non-steam applications need to be launched from game mode to get controller configurations, otherwise the desktop configuration will be used.