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Author_sort is a plain text field, not an is_multiple field, so commas aren't a problem.
Commas are significant for tags. That won't change.
Perhaps your users should use the authors-variant of the tags-like column. It takes names and, like authors, uses the '&' as the separator. Note that an is_names column respects the author_sort tweak when sorting on the tags browser.
To directly answer your question, there is no way to change the separator beyond the two you already have (comma and ampersand). That said, assuming you know the correct values, you could do what calibre does for authors (horrible hack) and change the comma to something else, then change it back when you create the collection. Calibre uses the vertical bar.
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