You won't be able to directly compare really, not with the same parameters anyway.
You're using the Express' analogue out, which means the Express has done a D to A conversion and amplified the audio a little to produce the analogue output. To see if there was a significant loudness difference you'd need to use the Express' optical out (you need a mini Toslink adapter to plug an optical cable into the same socket you use for analogue now).
If you compared optical from each you'd expect both to sound the same as they only hand the digital signal on to the TV.
In practice there are subtle differences - Express will output whatever file it was sent at 'CD quality' of 16 bit 44.1 kHz even if the source file was worse or better quality than CD. ATV2 for some reason converts audio to 16bit 48 kHz so the bitrate will be different and may cause some subtle audible difference - I wish it output at CD quality like the Express and ATV1.
One thing to bear in mind with Airplay - if you are doing Airplay actually from iTunes to AppleTV rather than accessing music from Computers section on ATV2 to access your library then any settings in iTunes such as volume, equalizer and audio 'enhancements', crossfades etc get applied to the Airplay stream. If you are playing from Computers>Your iTunes>Music on ATV2 however iTunes settings are ignored for the most part.
Another thing to check in ATV2's Audio and Video Settings is Sound Check - this limits dynamic range and generally makes audio sound awful - the Express does not have this feature (designed for headphone/earphone use or late night listening to avoid sudden high volume tracks). Turn Sound Check off ifit's on.
AC