I've only quickly examined the XML for this stuff, so it's possible I'm misinterpreting. If someone can confirm I'm reading correctly, I'd appreciate it.
In the covertoperations XML file, Establish Network has a 'basedifficulty' of 10. From the context of the file, it seems the success rate is 100-basedifficulty expressed in a percentage. So that would mean Establish Network has a 90% success rate.
Success rates seem to be:
*Establish Network: 90%
*Siphon Energy: 65%
*Steal Research: 65%
*Steal Technology: 50%
*Recruit Defectors: 50%
*Hack Satellites: 40%
*Coup D'etat: 40%
*Affinity Operations: 30%
Interestingly enough, the quest operations Deliver Dossier and Extract Operative (something I've never seen in game) have a basedifficulty of 0, meaning they should have 100% success rates. My limited experience is I have not seen Deliver Dossier fail yet.
As for Ops Support and Ops Recon: Ops Support shows an attribute called 'agentsurvivalpercent' of 1. Ops Recon has the attribute operationsuccesspercent at 1 as well. So it seems that ops support and ops recon don't really do much for spying.
Haven't found the counter-intel stuff yet.
Edit: Started looking in the LUA, which is unfortunately not something I'm proficient in reading. It might have more answers. What little my minimal programming expertise self can figure out right now is it seems the tech one receives from steal tech is weighted towards cheaper less expensive technologies based on your own research rates. Which means to get a better chance at stealing high end techs one needs to have a decent science rate already, making it difficult to simply 'steal the tech web.'