I am not sure exactly what you are asking to do, but as an example of storing "other kinds of stuff" in Calibre, I do this with the piano sheet music that I play. I store the music itself as a PDF (nothing new or different there), and I store a URL to a Youtube performance of it in the "ID" field of Calibre's metadata.
Here are two screenshots of what it looks like, one from Calibre, and one from a third party app named Calibre-Web that I use for my web service. The way I instruct friends that I have given access to, is first display the PDF via the "Read in Browser" link, then click on the "URL" link to hear it performed as they read through the sheet music.
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