Hitting this same problem in Kubuntu 20.04.
My case is this. In /usr/share/applications/defaults.list I had this:
application/pdf=org.gnome.Evince.desktop;google-chrome.desktop

I guess the trailing ";google-chrome.desktop" was in some way added by 
installing Chrome.
Firefox says my default PDF application is Chrome, while all the other system 
components (Dolphin, xdg-mime, xdg-open) correctly say that my default is 
Okular.

After editing /usr/share/applications/defaults.list to remove the
trailing ";google-chrome.desktop", now Firefox correctly knows my
default application for PDFs is Okular. No need to restart Firefox, the
change was immediate.

Strange enough, I don't have Evince installed, but many other file types
are associated with Evince in that defaults.list file. I guess Evince is
ignored because it is not installed. On the contrary, Chrome is
installed and so it's honored by Firefox, but in this case it's skipping
and ignoring my actual system settings for PDF file association.

So, there must be some problem here.

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https://bugs.launchpad.net/bugs/1551171

Title:
  /usr/share/applications/mimeinfo.cache is used for default
  applications in Firefox

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