Very happy to try to help Mark,
Yes, the change in capacitance is allowing a bit lower frequencies to reach the tweeter. Possibly enough to notice if you had changed from a new 4µF to a new 4.4µF if you were really in tune with the way your speakers sound, but I think that most people would probably not notice. And there will be a small peak where the tweeter is now playing at the same frequencies as the mid, but again a pretty small change.
The major difference in sound that you are hearing is undoubtedly because of replacing the 35+ year old very tired caps with new ones. It would be interesting to measure the old cap that isn't (quite) blown. It has probably drifted in capacitance, usually to a higher value in my experience, and easily to value that is actually more of a change from nominal than what happened when you put in the new 4.4µF. But what is worse is that the ESR of the old caps will easily have risen by several ohms.
I don't have any new NPE radial lead elcos on hand smaller than 18µF but I just measured one of those and got an ESR of 0.14 ohms. Smaller caps tend to have somewhat higher ESR so a 4µF might be closer to 0.5 ohm or a bit more. A MKP film cap will measure under 0.01 ohms usually. I would be surprised if that old cap is less than 3 ohms ESR.
One of the cool things about Xsim is that you can easily and quickly see what that change in resistance in a cap will do to your frequency response. You can hover the cursor over a cap in the schematic, right-click and select Tune in the pop-up menu. Click on the ESR entry and then simply use the scroll wheel to rapidly sweep through a range of resistances and the frequency window will show the curve change in real-time.
I just changed our prototype crossover to show a single 4µF cap with 3 ohms ESR. It drops the tweeter response by about 2db. Going to 4 ohms drops it by 3db.
What is also bad and can't be simulated is that those old caps will be leaking electrically internally, creating a lot of noise.
So it is not at all a surprise that you are getting much better sound. Going to a single 4µF MKP film cap for the tweeter will sound even better, but not as much of a difference as you just realized.
Just think what is going to happen when you replace the midrange caps.

Cheers,
James