Now I got it! I had the feeling I was somehow thinking of this in reverse. Today I had the time to sit down and figure this out, and I was right – I had been thinking that the name itself (e.g. "smtpd2") would need to be defined first so that parameters could be assigned to them in main.cf (how else would the system know what I mean with, say, smtpd2_client_restrictions), but in fact that name doesn't matter at all. The parameter name in main.cf can apparently be anything ("smtpd2_my_made_up_parameter_name=permit_mynetworks, permit_sasl_authenticated") as it is just used to relay that information to an smtpd instance in master.cf ("-o smtpd_client_restrictions=${smtpd2_my_made_up_parameter_name}").
Thanks Wietse and mouss! Postfix rocks! I'm migrating yet another SMB environment to Postix from Exchange after an excruciating weekend trying to get an Exchange 2003 installation straight.