This is kind of an odd question. Normally you add custom columns as needed rather than trying to figure out how to use them.
That said, here are some suggestions:
Subseries. (Series-like column) In my opinion, this should come with Calibre by default. There are a lot of authors out there who have a 2-level series for their books.
Hierarchy. (Or something similar. Hierarchical text column) If you're used to organizing your books as files in folders, it can help ease the transition to Calibre if you use a custom column to simulate this system. And contrary to what the manual says, you CAN store your entire folder structure in a single field and create a save-to-disk template that will export it properly.
Since you're into fan fiction, there are 2 more columns you probably want to include:
Original Author. (Author field) Store the author of the original series that the fan fiction was based upon.
Original Series. (Text field) Store the series that the fan fiction was based upon.
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