Have a look at these tutorials available on the Skyline website, or within Skyline itself:
Small Molecule Method Development and CE Optimization
Hi-Res Metabolomics

One difference from the workflow in these tutorials is that they start with a transition list, it sounds like you will want to start with the ,msp spectral library. For that you'd use the Skyline menu item "View | Library Explorer", then add the .msp library, then use the "Add All" button to add the precursors and fragments to your Skyline document's Targets tree. After that it's the same - extract chromatograms) for the targets ("File | Import | Results", see which targets give strong signa's, refine, export method, iterate on that.

Thanks for using the Skyline support board,
Brian Pratt