Are you asking if Skyline can identify the compounds? If so, the answer is no, Skyline isn't built for that.
If you do know the compound associated with a chromatogram in Skyline, you can set its name with a right click in the Targets tree, and selecting Modify.
But the most convenient route is to start with a proper spectral library. I'd say keep looking for a usable library - NIST is not the only source for those.
Thanks for using the Skyline support board,
Brian Pratt