Physical chemical property that determines redox potential?
As I understand it, the potential is related to the difference in energy between the oxidized and reduced state (via the Gibb's energy as Mithoron noted). While their individual electron orbital energies are probably similar given the similar nuclear charges, the oxidized and reduced states are differently occupied and so have different energies.

In zinc for example, you have the reduced state of 4s2, 3d10 and oxidized state of 3d10. Copper on the other hand goes from 4s1, 3d10 to 3d9. $\ce{Zn^2+}$ has a fully occupied d-shell while $\ce{Cu^2+}$ does not, meaning that the reduced state for zinc is lower energy and more stable. As a result, zinc has a stronger tendency to oxidize and consequently a lower reduction potential.