Short answer, yes it does matter which wire you pair with which -- if you're making two runs out of the 4 conductors.
If you think of star quad as 4 conductors arranged in a square and then the whole bundle twisted, and the conductors oriented on the ordinal compass points of north, east, south, and west, you want to pair the north and south together, and the east and west -- this keeps the capacitance and inductance "balanced" with respect to the other conductor.
If they were twisted pairs that were then twisted together -- typically with each pair twisted in different directions, and then one conductor of each pair connected to one from the other pair, I believe that is a molloit braid -- similar to the way that the BH power cable hot and neutral leads are arranged.
HTH,
Jim
Jim Rebman -- recovering audiophile
Equitech balanced power; uRendu, USB processor -> Musette DAC -> 5670 tube buffer -> Finale Audio F138 FFX -> Cain and Cain Abbys near-field).
s.e.x. 2.1 under construction. Want list: Stereomour II
All ICs homemade (speaker and power next)