Competent Colt revolversmiths are rare these days, especially for the older style actions such as Det. Special, Diamondback and Python. Most of the big names have retired or deceased (Jerry Moran, Austin Behler, Fred Sadowski, Reeves Jungkind). The ones I can think of are the following:
Cylinder and Slide in Nebraska
http://www.cylinder-slide.com/Grant Cunningham
http://www.grantcunningham.com/ (does old style actions only)
George Wessinger
http://www.americanpistol.com/Members/wessinger.htmlAlan Tanaka
http://www.americanpistol.com/Members/tanaka.html (some Colt work)
Walt Sherman 5846 Tea Rose Trail, Tallahassee, FL (904)878-9563 (Python roller action tunes)
The older style Colt actions due to design stack in double action pull. This can be changed to a straight through pull as on a S&W or Ruger via various different methods. On the older style actions usually there are 2 different level of tunes. The first smooths the internals and reduces the trigger pull but does not address the stacking. The second sometimes called a "supertune" also addresses that(along with things such as headspace and firing pin protrusion) but is of course more expensive. The newer design guns employ sintered metal and/or MIM parts and do not have the hand fitting to the degree of the older ones. Less is or can be done to these but a notable difference can still be made. As you note Colts are becoming worth quite a bit more now that they have ceased all revolver production (and perhaps destroyed the tooling). Because of this I would only use a known gunsmith. Colts have for a considerable time been outside the repertoire of the local village gunsmith.
With tuning the Python will have the lowest double action pull ( perhaps 6 pounds or less double action and 2.5 single). The newer models will be nowhere as light nor as smooth (the short hammer arc on the new models requires higher spring pressure). The smaller, older models such as Detective Special while having a similar action to the Python do not have the leverage due to size so will require somewhat heavier springing. I would estimate a supertuned Det. Sp. would have a double action of about 7.5 to 8 pounds. The newer model medium frames probably could be tuned to about 8-8.5 pounds double action.