Ignoring the ResolveUsing overloads that take an IValueResolver, and looking only at these 2 methods:
v
MapFrom has a few extra smarts. For example (from the mailing list):
In MapFrom, I try to be smart about digging in to child properties (much like the normal flattening does). MapFrom is an attempt to mimic flattening, with an added bit of allowing redirection. ResolveUsing doesn't have this behavior.
I'm not sure if this is fully documented anywhere (apart from in the source code).