The solution ended up being fairly simple:
First, define a custom GeomvalType, inheriting geoalchemy2's CompositeType and specifying a typemap specific to geomval:
class GeomvalType(ga2.types.CompositeType):
typemap = {'geom':ga2.Geometry('MULTIPOLYGON'),'val':Float}
Next, use type_coerce to cast the ST_DumpAsPolygons result to the GeomvalType in the initial query:
q = session.query(type_coerce(ga2.func.ST_DumpAsPolygons(my_raster_table.c.rast), GeomvalType()).label('dap'))
Finally, access it (successfully!) from the subquery as I was trying to before:
q2 = session.query(ga2.func.ST_Area(q.subquery().c.dap.geom))