"My preamp has an output impedance of 5k ohms, making for a possible poor match with the sub (20K input Imp.) if I use the 2nd outputs on my pre into the sub's RCA inputs."
You can add a SS Buffer ... 1 to 1 gain amp ... to 2nd output on preamp to lower the preamp's output impedance to better match your sub's 20K input
The Buffer should not add any gain but lower the impedance of the preamp from 5k to less than 600 ohms
With a 5K output I would guess the pre is Tube .. how is match to main amp ??
"I suppose I could hook the sub up by going from my amp to the high level inputs on my sub?"
I wouldn't daisy chain if I didn't have to ... keep the main amp and speakers seperate
"I could simply run a second set of speaker cables out from my amp to my 2 subs this way right?"
Then the main amp would have to drive both the main speakers and two subs ... may be to much of a load to ask your amp to drive ...