I might be mistaken, but I don't believe that the Dewey classification is held in a book's metadata as standard. Assuming that I'm right:
(a) you'd need to add it yourself; but
(b) this would be a simple matter. If I wanted it, I'd do it by creating a new column in Calibre (Preferences/Add your own columns) and putting the Dewey number in that. There might be other ways of handling it.
Once that column exists, sorting it numerically is a trivial matter.
(The merits, or otherwise, of the Dewey system are an entirely separate issue.)
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