EDIT 4, 5 and 6
8 hours in, any more ideas are welcome :) Maybe this bug is already known and solved, but I get the behaviour I described in edit 2&
To keep things simple I like to use the .css.scss exstension and use:
.css.scss
li { background-image: image-url("logo_80px_80px.png"); }
Full reference can be found on Rails Guides under Section 2.2.2.