The signal that's being sent from your Mac is a digital signal so it has to be converted to an analog signal somewhere along the way. The Airport Express will do it for you but it was not designed as a high-end audio component and it's much better to hand that task off to a device that is designed specifically for it.
Most DAC's do have a Toslink input, but not all, so check that before you buy something. The same stereo-mini outlet you're using now for analog output will also accept a Toslink cable with a mini-Toslink connector, or you can use a standard Toslink to mini-Toslink adapter on a standard Toslink cable. Most DAC's that accept Toslink will use a standard Toslink connector on that end. So, you'll need some combination of cable and/or adapter that gives you a standard Toslink connector on one end of the cable and a mini-Toslink on the other.
A search of the site will probably give you some good information about DAC's to investigate.
Most DAC's do have a Toslink input, but not all, so check that before you buy something. The same stereo-mini outlet you're using now for analog output will also accept a Toslink cable with a mini-Toslink connector, or you can use a standard Toslink to mini-Toslink adapter on a standard Toslink cable. Most DAC's that accept Toslink will use a standard Toslink connector on that end. So, you'll need some combination of cable and/or adapter that gives you a standard Toslink connector on one end of the cable and a mini-Toslink on the other.
A search of the site will probably give you some good information about DAC's to investigate.