The configuration would go like this:
PC --> DAC 1 --> L, R speakers
--> DAC 2 --> Subwoofers 1 and 2
On the PC, download
VB Audio Matrix. Enable the virtual ASIO channel. Set it up to output channels 1, 2 to DAC 2 (i.e. to the subwoofers 1 and 2), and channels 3, 4 to DAC 1 (i.e. to L, R speakers). Make sure the microphone is recognized by VB Matrix.
Open REW and set it up in ASIO mode to output to VB Matrix. Select the appropriate microphone channel.
Then you need to take some timing measurements. Set REW to use a timing chirp and set this as your left speaker (i.e. channel 3). Now do sweeps of the subwoofers at the listening position. REW will automatically tell you what the delay is with respect to the timing chirp, but you can check by overlaying the impulse responses (aligning all the impulses with the tweeter chirp) and measuring the delay manually that way.
Then you need to figure out how to make a filter that will delay the subwoofer appropriately. I use a different tool for this, so I can't talk you through the REW procedure.
Load the filters into the playback software of your choice. It will need a built-in convolver.