Apparently this turned out to be a topology problem with just one of the polygroups in the mesh.
Here is the polygroup in question (split from the full mesh):

… at lowest subdiv, Zbrush finds full symmetry on this and will allow poseable symmetry – but you can clearly see the problem.
Smart resym shows full symmetry found, Resym X shows 97.20994% symmetry points found. Neither operation moves the points, so that’s the problem. As soon as you subdivide, it won’t map poseable symmetry.
The only way to fix this is to Mirror and weld X.
The only thing I don’t like about using mirror and weld is what it does to my UVs/texture map – but I’ll use another thread for that.