"the expression for the logarithmic integral"
While there is an asymptotic expansion for the logarithmic integral of the form you propose it is not convergent. It is only a good representation of li(x) for a certain number of terms depending on x.
Other series for li(x) that do converge are much trickier. For example Ramanujan's series:
http://en.wikipedia.org/wiki/Logarit...representation.
Pi(x) - Li(x) = (Difference of Pi(x) - Li(x)) (see wiki on RH for the best estimate on this) + (Error on your expression for Pi(x)) + (Error on your expression for Li(x))
Note that I added the errors because the sign of the errors is not known. If you could prove the errors are strictly positive you could subtract them.
Of course everyone wishes that such a nice analytic series exists for Pi(x). Many eminent mathematicians have been looking for such a series for hundreds of years with not much to show for it.