If the Digital to Analog Converter (DAC) in your receiver is better than the DAC in the Airport Express, a digital optical connection may provide better audio quality. See this test report in Stereophile magazine:
http://www.stereophile.com/accessoryreviews/505apple/
An optical connection also provides isolation from ground loops and other electrical noise that can effect the analog output of Airport Express.
There is one potential problem with using the Airport Express optical output. Most receivers and preamp processors require a certain amount of time to synchronize their DACs with an audio bitstream. Most digital audio components send a bitstream of digital silence whenever the component is turned on, so the receiver's DAC is synchronized before the audio program begins to play. Unlike most digital audio components, the Airport Express digital audio output is inactive until it receives an audio bitstream. This anomaly can cause a momentary loss of audio each time the bitstream is initiated.