Not exactly. Default configuration for ASTRO 25 systems is to rotate through the traffic channels to balance the load on the repeaters. The BSI channel is normally the most protected, followed by the alternate control channels, which are used for traffic only if the normal non-protected traffic channels are already in use. There are always going to be exceptions to the rule, and some of it depends on how many channels are at the site, if data is provisioned, whether FDMA, TDMA, or DDM is in use, how each channel is provisioned as far as being data and/or voice capable, etc.
So yes, there is a hierarchy, but that primarily applies to channels with a specific purpose such as control-capable and the BSI channel on most run of the mill ASTRO 25 systems. It is possible to have some fairly complicated setups when you start getting into systems with DDM and data enabled, where you'd want to steer certain traffic to particular channels at the site.