It has to do with the nature of App Cache itself.
You specify a manifest file that lists all the static assets required for your app to run offline. You don't have any programmatic access to the cache to add and remove files via JS.
So for a node-webkit app, it'd make more sense to fetch these files and store them in the Application Support folder (Or AppData, depending on the platform). That's where the node.js part is really useful, the file IO stuff.