I started with a CNC partly because I was interested in PCB isolation routing. I've actually switched to UV exposure - partly because I wanted to try it and partly because routed PCBs have far more "contour" compared to etched ones and it makes solder mask application harder.
Answering your original question, I don't think PDF to g-code will work particularly well. If you really needed to then something like inkscape might be able to trace the outline into a vector format. I can't imagine the results would be great but you could at least give that a try. Once you have a reasonable vector it would be possible but you'd be in rather unique territory.
Having said all that, I would thoroughly recommend CNC stuff as yet another expensive time consuming hobby!