I ask Alexa for a particular playlist...for example, "play my country playlist" or "play my Les Miserables playlist".
For a particular song, I say "play xxx from my library". If I want a station, I say "play 820 WBAP" or "play 570 KLIF". I'm not familiar with "default station services" so I might not be answering your question correctly. I only have one library but have created a few playlists from songs in my library.