As Devrij said, if you've rebound your recenter button, it should work in the start menu (and I'm fairly sure it should even work on the loading screen). If you've rebound that option and it's still not working, then there's something weird going off.
It shouldn't matter where you're launching the game from (Frontier launcher, Home, Steam) but if you do launch it form Oculus Home it is set up straight away to go into VR mode, so you don't have to initially set anything from the menus. I have it running from Home because it was just easier after a Windows reinstall to pick it from the Home menu, rather than go and grab an extra game installer.
Edit - noticed you just replied to Devrij. At this point, I'd seriously consider uninstalling, make sure you delete any left over Elite file/folders, and reinstall from Home. You really shouldn't be having an issue recentering.