The successful miniaturization of extremely accurate atomic clocks invites prospects for satellite missions to perform precise timing experiments. This will allow effects predicted by general relativity to be detected in Earth's gravitational field. In this paper we introduce a convenient formalism for studying these effects, and compute the fractional timing differences generated by them for the orbit of a satellite capable of accurate time transfer to a terrestrial receiving station on Earth, as proposed by planned missions. We find that (1) Schwarzschild perturbations will be measurable through their effects both on the orbit and on the signal propagation, (2) frame-dragging of the orbit will be readily measurable, and (3) in optimistic scenarios, the spin-squared metric effects may be measurable for the first time ever. Our estimates suggest that a clock with a fractional timing inaccuracy of 10-16 on a highly eccentric Earth orbit will measure all these effects, while for a low Earth circular orbit like that of the Atomic Clock Ensemble in Space mission, detection will be more challenging.