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It's a bit more complicated than that. The most important factor is the speaker's sensitivity.
Take a Celestion Vintage 30 and compare it to a G12T75. Both have a similar wattage rating (60 vs 75) but at any given amp setting, the Vintage 30 sounds louder. That's because its sensitivity is 100db/watt, which is 3db more than the G12t75. That's the same volume difference as you'd get by doubling the power of your amp. So by switching from a 75 watt speaker to a 60 watt speaker, you give yourself more volume.
All the wattage rating tells you is the maximum wattage you can safely put through the speaker before it gets too hot or pushes the cone too far and breaks it.
However, what speakers do as they approach their maximum wattage rating is that they begin to compress and colour the sound, and turn some of the energy your amp is putting out into heat instead of sound. So if you have, say, a 50 watt speaker in a 50 watt amp, you could get more total volume by switching to a 100 watt speaker of the same sensitivity because it wouldn't be wasting so much of the energy as heat.
So really, getting more volume out of your amp is about increasing the sensitivity of the speaker, and making sure that you're not driving the speaker into compression. In your case, you already have plenty of leeway with your 66 watt speaker, you're probably not driving it into compression most of the time. So switching to a 100 watt speaker wouldn't give you more volume, unless it was a more sensitive speaker.
Hope that helps!
Originally Posted by telephant
Tone is really half the argument. We both know ultimately it means nothing. Write a song. Write. A ****************ing. Song.