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The tags are stored in what can be considered a random order, and are sorted in that order. Thus, the resulting order of sorting on tags is equally random. However, it is repeatable.
My belief is that the tags are sorted in the order they were added to calibre, not to the books. This isn't much help, though.
If you want known sorting behavior, then you must use single-value columns. The custom text type column is good for this.
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