Hi,
I've used (and still using) a lot LTspice
http://www.linear.com/designtools/software/ to check a number of quantitative data about a given circuit such as frequency res., biasing, gains, shape of clipped waveforms etc. before actually build anything.
I applied this mainly to dist./fuzz, but also compressors.
Example: I have entered in LTspice a modified Shredmaster schematics (my favourite pedal) I built and I've been using since five years. Then, I recently build a modified version of the Tube Driver that relly did not cut through, so I used extensively simulation to adjust the pre and post clipping (tubes) stage signal frequency shaping to match the "reference" Shredmaster behaviour. I was amazed about how similar the two pedals sounded similar once I adjusted that parameters.
A word of warning: the models available do have limitations (that add up to mine... )e.g.
1) I failed simulating Ge biasing and leakages thermal behaviours (I've never achieved a reliable simulation of simple Ge FF !)
2) I could not find suitable models for simulating properly starving plate tubes circuits . Grid current vs, Anode voltage dependency for low anode voltage value is usually not or wrongly taken into accout by the availble models.
One last thing: LTspice can be fed by .wav files, so you can virtually "ear" the circuit characteristic in simulation.
I've never got the time to explore this possibility which IMO has limited practical value anyway
Best Regards,
lcv