You need to brush up on how epubs are constructed. You need to use css to define various font-faces and use css selectors to apply them to the various html elements. Then you need to consider whether to embed the fonts in the epub, or to provide fallback generic font-families in case the readers you're targeting don't have the specific font you designated. If you choose to embed the fonts, you also need to consider a font's licensing terms.
Regardless... how to specify different fonts for your EPUB isn't really a Sigil-specific topic. It's more appropriate to the EPUB forum in general.
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