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Convert/Export as RTF from Calibre and then use a dedicated PDF generating tool or wordprocessor. Then you can easily change styles.
PDFs are electronic proofs of pages, not ebooks.
I'd load the RTF in Word or LibreOffice, style/format and then use whatever PDF creation tool you have you like (You can create PDFs from MS Word or LibreOffice Writer direct). Watch out for Word's last line of paragraph before a page break error. Add an extra return and then backspace to cure a last line being stretched out (fully justified). I don't know why that bug is there so long, but it shows up on PDF export or print. That's the official MS workaround. Or use LibreOffice Writer!
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