Now to the question, how do I know which of these masses represent vitamin D and its metabolites? Is it just a matter of freely searching for the masses of vitamin D and its metabolites and starting from that?
Did you acquire MS/MS data too? If so, you can check which precursors show fragment ions that are similar to those obtained for vitamin D. At the same time, fragmentation spectra can also point towards how the additional compounds differ (chemically) from vitamin D.