Try lowering you desktop resolution; that should get the game to try starting in a lower resolution, which may allow it to load, and create the configuration files.
Try starting the game directly from the '..\SteamApps\common\Divinity - Original Sin\Shipping\EoCApp.exe' program file (or similarly for the GOG version), by right clicking and running as administrator.
Are you shutting down all non-essential programs (especially anti-virus) before trying to start the game?
Dropped it to 1024x768 and same thing happens. Ran from Shipping directory and same thing happens. Disabled Anti-virus and same thing happens.
What is this level cache folder? I don't see it anywhere.
