I've never tried this myself, but you can get it to start when windows starts. Got to options > advanced > integration and tick Start Keepass at Windows Startup. For reference I am using the non-professional (classic) edition v1.28. Then if you create a database that uses a key file only and make sure the file is always accessible this should work. You can also set Keepass to open the last used database on startup which should then make it seamless.
This kind of defeats the purpose of securely storing your passwords in my view though, as anyone who knows your Windows password will then have access to your Keepass database.