OK, first thing you should do is install drkaii's excellent EDProfiler which will allow you to configure different profiles (including graphics settings, key bindings and HUD colours) for your VR and non-VR gameplay.
https://forums.frontier.co.uk/showt...er-Robust-Settings-Profiler-Switcher-Detector!
The thing which determines whether you get VR gameplay is setting 3D to "HMD Headphones" so you'd create two profiles, one with that set and one with 3D set to "none" (or whatever the non-HMD option is, can't remember exactly). Then what you do is start EDProfiler, select whichever of the two profiles you want, hit Apply and then run the game from your desktop shortcut as normal.
Now ... that said, even when you're running a 2D profile, Oculus Home will still start up. You can prevent this happening if you want by stopping the OVRService Windows service. What I do is to have two desktop shortcuts, one labelled "Stop Oculus" (which is a shortcut to the command 'net stop OVRService') and another labelled "Start Oculus" (which is a shortcut to 'net start OVRService'). Stopping the service will also prevent the Oculus switching itself on if anything happens to come near it's proximity sensor (e.g. I store mine in a fleece bag which was always setting it off).