Any tags you enter in Calibre's tags column will auto sort into Collections on your reader. Multiple tags allows the same book to appear in multiple collections.
If you mean how do you sort collections: They are in alphabetical order.
If you mean how do you sort books in a specific collection: Same as on your bookshelf. Click on the AZ button at the top and you can sort books in that collection by added order, date, title, author or filename.
IF you mean you want books in your "Books" list to be sorted by collection, you cannot.
I THINK what you want to do is go to the Tags in Calibre, click in that column and add a collection name like "Harry Potter Novels". That's it. Once the books are on your reader, go to the "Collections" area and they'll be grouped together.
Frankly, I have found that if you add books in a series to the Reader, one at a time in order and then go to the "Books" section and select "Sort by Author", the order for the book series will be correct.
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