Streaming either wired or wirelessly from a Mac to the Airport Express, then via the optical mini-Toslink jack on the AE to an optical input on a DAC works very well.
That does, indeed, bypass the internal DAC of the AE and there is no impact on Apple Lossless files.
The usual recommendation is to use a glass Toslink cable, I have one I bought from an audiogon member who no longer sells them here but there are other sources, I've seen the Sonicwave cables sold on Amazon recommended highly.
If you're going to stream wirelessly it's definitely worth ensuring that both the Mac you use and the Airport Express you get have 802.11n capability, rather than the older 802.11g standard. Newer ones all do and that helps ensure you won't have interference issues.