PeakView® Software is a data exploration tool and allows spectra to be viewed and interpreted, including the ability to match a reference library spectrum to your current spectrum. There is additional associated software called LibraryView™ Software which enables a user to build their own database of compounds/metabolites and add their own acquired spectra of known standards or purified material. The *.wiff files do not need to be converted to build the database; you simply open the spectra for your compound of interest in PeakView and add it to the LibraryView database.
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Regarding other databases, LibraryView allows searching of ChemSpider which links to a number of online databases such as PubChem, HMDB, LIPIDMAPS, KEGG, etc. Libraries available from SCIEX can be searched here too, such as the accurate mass metabolite spectral library (AMMSL), the pesticide library, the drug screening or mycotoxin libraries, etc. and each of these libraries can be added to with your own library.
Once you have your database ready, you can use MasterView™ Software (separate installer, installs into PeakView) to automatically ID and quantify analytes in your data using predefined libraries. MasterView allows you to open all your MS data files and search the MS and MS/MS data using your own database, the SCIEX libraries, if installed and/or ChemSpider simultaneously and confidently identify your metabolites.

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