At the software level both serial and parallel DCC are just PPP. There's an exchange at the beginning where one side says CLIENT and the other says CLIENTSERVER (don't remember exactly which order) but then they just switch to PPP, so it's something you can handle with a chat script. There are Linux HOWTOs out there walking through how to set it up for serial.I've used DCC over a serial cable in the past. Installed Office 95 through it, not recommended. Slow as molasses, but worked reliably...
On a different note: Does anyone have a good description of the DCC serial wire protocol? Since it is part of Windows, it would be a decent way to connect to modern machines if there was a decent client on the other end. Especially since it supports TCP/IP as well.