I would think that using a string that you later must parse and sort would be too intensive on any system. Instead, let the database do what it does best -- store, sort, and index data. I've never done it before, but if you use two columns (for each userid), you could also inherently store which friend made the friendship request (FromFriend, ToFriend). You can even put a status column to indicate what stage that friendship is in (requested, accepted).
Hope that helps somewhat.