Yes, per 2020 NEC 300.3(B)(1), you need to have a balanced set of conductors in each raceway.
Yes, with only one raceway, there's no need to coordinate the parallel'ing details between different legs/neutral, so the load calc will dictate what you need. For a crazy example, on a 3P4W 240V/120V delta (high leg delta), depending on how the load calc works out, you could use 2 conductors for the high leg, 3 conductors for the other ungrounded conductors, and 1 conductor for the neutral. [Maybe that's not so crazy, since that's what you get if you overlay a 2 set 3P3W supply with a 1 set 1P3W supply.]
BTW, with 4 CCCs in the conduit, each 4/0 Al is good for 205A * 0.8 = 164A if no temperature correction is required. So if there is a single service OCPD, it would need to be 350A or less. [Even on a residence with the 83% factor, 164*2/0.83 = 395A, too low for a 400A OCPD.] If you have two separate service OCPDs, they would each need to be 175A or less. Unless of course an exemption from derating applies, like less than 24", or less than 10' and less than 10% of the total run, where in the rest of the run you do separate out into fewer than 3 CCCs per conduit/cable.
Cheers, Wayne