Not using libspotify, no. Since you can log in to an account using libspotify on any computer, paths are meaningless - in fact, they never end up in the backend and the paths you can sort-of get from the desktop client are locally resolved ones.
For local tracks using libspotify, you need to ask the user where their local files are stored and dynamically resolve them yourself. The track URIs for these tracks contains basic metadata and a duration, which should be enough to find the track in question.