GeoServer's Virtual Services allow you to have separate WMS, WFS, etc. services for subsets of the catalog. This feature is currently tied to workspaces, which is why a layer can only be in one Virtual Service (and in fact must be in one virtual service.) I think the integration between layer collections and virtual services is pretty obvious - make a workspace for each collection and assign the workspace for each layer according to its collection. But as I said, without changes to GeoServer this comes along with probably unacceptable technical limitations.
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David Winslow