NONE of the cmyk inks used for printing 4 color process, are part of the formula for mixing any spot PMS colors. Process black could be substituted for PMS black in a pinch with the understanding that the process black will lack the neutrality of the PMS mixing black. Process black usually has a reflex blue like component, to add a bit of density to type and black halftones. If your printing a 4 color job, with many black halftones, where your looking for an older style neutrality, such as in black and white photography books, sometimes PMS black will get you where you want to be. Cyan is close in hue to PMS process blue, although with not as much strength. Magenta usually has a strong rhodamine red component but interchangeability is something I would caution. Process yellow is pretty close to PMS yellow, and would probably be the most interchangeable mainly because of the humans eyes weakness in the perception of yellows.
It would go without saying, that if you were to use any of the mixing inks when printing 4 color process there may be tack adjustments required.
As far as using 4c process inks mixed together I know of no standardized formulas or mixing guides.
Dinkman would be a better source of information on this topic.