It's recommended that you head to take on John Seed first at Fall's End in Holland Valley. You'll need to have drawn out and defeated one of main villain Joseph Seed's brothers or sisters to get it. While it costs a lot, despite its position on the Perks page remember that Far Cry 5 doesn't have a linear unlock tree - so the moment you have 8 Perk Points you can unlock it straight away. Check out our Perks Guide on how to get Perk Points quickly. It costs a very expensive 8 Perk Points, but is certainly worth it.
Weapon Slot 3 can be unlocked by buying the 'Additional Holster' Perk, seen above, in the Prepper type of the Perks menu.