I have several Airport Express N units. Although I do not own an Apple TV, there has been a bit written about the fact that the Gen 2 Apple TV resamples everything to 48KHz. The previous Gen 1 Apple TV and both Airport Express (Gen 1 wireless "G" and Gen 2 wirelesss "N") do not resample 44.1KHz files.
Some report they do not hear a difference in systems with modest amplification and speakers. Others say they do hear a difference, and some others just have a problem with the device mucking with what was a previously bit perfect translation of their 44.1KHz Redbook files.
Obviously the ATV adds video streaming capability, but if video streaming is not needed, some other differences that might prompt one to choose one over the other are:
1. The Apple TV does not have an internal DAC whereas the Airport Express does. If you are going into an external DAC or AVR anyway this won't matter, but if not, I find the AEX internal DAC to be more than acceptable for casual listening.
2. The Airport Express can function as a wireless router and provide the connection to an Internet modem, albeit with the limitation of only one wired Ethernet LAN port and less range than the Airport Extreme router.
3. The Airport Express can function as a wireless print server when connected to a USB printer.
Steve