I think the most important point is consistency, which comes in a couple of flavours.
PrimeFaces (PF) components have a lot of styling put on them (through the theme options). If you use PF components throughout your application, you'll get a consistent style. If you mix PF and JSF components this will look messy.
PF components have a particular way of doing things - organising options, defining ajax calls etc. While it's important to know how the JSF stuff works underneath, using PF components consistently will make your code consistent too.
Finally, in many cases PF components are exact replacements for JSF components, but often with extra features added. There's no reason not to take advantage of them.