Although I use CSS in QT a lot I still have concerns about if extensive CSS is a right thing to do in Qt..
I would strongly suggest try to limit CSS usage or at least think very carefully then designing them..
Especially for complex application with a lot of controls and complicated layouts you should be very very careful in using them if you target cross-platforms environments. It's indeed very fast way to go if you need to 'paint' nicely an application targeting only Win32 or MacOSX for example, but running same CSS on other platform could result in even more uglier UI then using native controls.
Then you start working on interfaces where 'each pixel matters' you will see that even basic layouts in Qt has mistakes and adding on top CSS engine which also full of 'small' bugs could lead to even more unpredictable results and development time.
Regarding your question - setting a global CSS on an application level is a fastest thing you can get, BUT remember that it will be inherited within all application widgets so in case you need something different you will have to create special rules.