<< Wouldn't the primary source of capacitance on a PCB be due to neighboring wires? >>
In high RF situations, there is a ground plane on the PC board, either on the back, or one of the layers.
If you keep the traces the right width, and the right distance from the ground plane of the right material and properties, the major capacitance is to the ground plane, not other traces.
I remember some talk at Moto of a PC board material called epsilon 10. Granted, this was 20 years ago, but it was then an exotic PC board material that they considered for some of the RF sections.
Doug