Chebfun is a lot more full featured, and ApproxFun is _very_ rough around the edges. ApproxFun will probably end up a very different animal than chebfun: right now the goal is to tackle PDEs on a broader class of domains, something I think is beyond the scope of Chebfun due to issues with Matlab's speed, memory management, etc.
Here’s a partial list of features in Chebfun not in ApproxFun:
1) Automatic edge detection and domain splitting
2) Support for delta functions
3) Built-in time stepping (pde15s)
4) Eigenvalue problems
5) Automatic nonlinear ODE solver
6) Operator exponential
7) Smarter constructor for determining convergence
8) Automatic differentiation
I have no concrete plans at the moment of adding these features, though eigenvalue problems and operator exponentials will likely find their way in at some point.
Sheehan