You cannot store any files in the calibre library unless you are willing to give them their own extension and make them a format. And that will just confuse your users. Store your wordlist in the db, your life will be a lot simpler. If you put random files in calibre library folders they will be deleted automatically if the user chanes title or author and check library will complain about them.
Quoting the documentation:
A val_map is just a python dictionary, like this:
{book_id:"some value", book_id2:"other value"}
Yes, I was refering to providing an interface for your users to edit the stored data, which can happen only in a user interface plugin.
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