Hi skyline - I think I'm in a pretty good position to advise here as I was previously using an Airport Express to stream directly to my SuperNait via the optical out.
I can thoroughly recommend the SuperNait, and Neat speakers make a great partner, however I would not recommend using the AE for 2 main reasons.
1. it is very prone to wireless interference when playing music - some people are lucky and are not affected , but if you are then it can be a long and painful road to try to eliminate it. This can be interference that you're not even aware of and would normally just cause a momentary slowing of your wireless bandwidth that you wouldn't notice, but as soon as you try to stream music...
2. This is the most significant one - the AE digital output has very poor adherence to the SPDI/F specification and the timing of the digital data stream can vary outside of tolerance and cause problems with the DAC it's connected to. When I had mine connected to my SN i would get 'blips' where the sound would cut out momentarily and then back in again*. Very annoying and absolutely nothing you can do about it.
*I went through a very long and complicated process to distinguish this from the aforementioned wireless interference, but it was definitely a separate issue. I've seen threads on here with people suffering the same effect using Cambridge and Cyrus DACs.
Whatever amp/speakers you go for I recommend Sonos for streaming your music. It's designed mainly as a wireless multi-room streaming system, but it works perfectly well in just one 'zone'. The interface is outstanding and the quality connected via digital coax is better than AE or my macbook connected directly to my SN via optical.
Granted the Sonos route is much more expensive - £280 for a ZP90 zone player and you'd need to add a controller to this - you can use an iPhone or iPod Touch if you have one or you could buy the CR200 controller but that's steep at £280, or you could do what I did and see if you can find one of the older CR100s cheap on ebay. Or if you have a laptop then you can use the controller application for that.
The Sonos system creates it's own wireless network so it's far less susceptible to interference. I've got my ZP90 connected via ethernet, but if you don't have your router close enough to your hi-fi to do that then you'll have to buy a 'Zonebridge' (£80), as you need to have one Sonos component connected to you router via Ethernet and it's this that is the first link in the Sonos network.
There are alternatives to Sonos - Logitech's Squeezebox range being the obvious one - you would probably be able to something squezebox-based a bit cheaper.
Anyway - I hope all that is useful. If I could boil all the above down to a single piece of advice then....do not rely on an Airport Express as part of the primary source in your main system.