It actually depends on the individual specimen. You probably know the V came out first, and the IV followed. The IV is said to be made with unselected parts, while only selected parts go into the V. So if you're lucky, you may get a Series IV just as good as any Series V. There are some small differences in function - there is a VTF wheel on the V, and the thumbscrew on the counterbalance is just used to balance the arm before setting VTF. There is a damping trough by default on the V, and it is an add-on for most IV arms (I think the IV.VI also has the trough standard). Finally, there is a VTA screw to allow fine adjustments of tonearm height whilst the mounting clamp is loosened.
I have one Series V, two Series IV, a 309 and two M10 (a simpler arm made for the Model 10) arms. If I compare the V with the M10, I can certainly hear a difference, but I'd be hard pressed to hear the difference between the IVs and the V.