For a complete asymptotic up to $o(1)$ I get
$$S(n) = \frac{1}{2} \log n + \frac{\gamma + \log 2}{2} + o(1).$$
Your sum $S(n)$ is very close to the sum $Q(n) = 1 + \frac{n-1}{n} + \frac{(n-1)(n-2)}{n^2} + \cdots = \sum_{k \geq 1} \frac{n^{\underline{k}}}{n^k}$ considered in Problem 9.56 in Concrete Mathematics and elsewhere in Knuth's work, so I've adapted some of the arguments I found there.
Let's consider the sum $S'(n) = \sum_{k \geq 1} \frac{n^{\underline{k}}}{k n^k} = S(n) - \frac{1}{2n} = S(n) + o(1).$ In the answer to Problem 9.56 in Concrete Mathematics the authors indicate that Stirling's approximation can be used to show that if $k \leq n^{1/2+\epsilon}$ then
$$\frac{n^{\underline{k}}}{k n^k} = e^{-k^2/2n} \left(\frac{1}{k} + \frac{1}{2n} - \frac{2}{3} \frac{k^2}{(2n)^2} + O(n^{-1+4 \epsilon})\right).$$
Then, Knuth and Pittel, in "A Recurrence Related to Trees," (Proceedings of the AMS 105(2) 1989, pp. 335-349) indicate this means that $\frac{n^{\underline{k}}}{k \, n^k}$ is exponentially small when $k \geq n^{1/2+\epsilon}$ and so can be replaced with other exponentially small terms to get
$$S'(n) = T_{2n}(-1) + \left(\frac{1}{2n} + O(n^{-1 + 4 \epsilon})\right) T_{2n}(0) - \frac{1}{6n^2} T_{2n}(2),$$
where $T_n(x) = \sum_{k \geq 1} k^x e^{-k^2/n}$.
Lemma 1 in the Knuth and Pittel paper then states that if $x > -1$ then $$T_n(x) = \frac{1}{2} \Gamma\left(\frac{x+1}{2}\right) n^{(x+1)/2} + O(1).$$ They also mention that a derivation of $$T_n(-1) = \frac{1}{2} \log n + \frac{\gamma}{2} + O(n^{-1})$$ is in Knuth's Art of Computer Programming, Vol. 3, Exercise 5.2.2-4, as part of the analysis of bubblesort.
Putting this all together gives us $S(n) = \frac{1}{2} \log (2n) + \frac{\gamma}{2} + o(1) = \frac{1}{2} \log n + \frac{\gamma + \log 2}{2} + o(1).$
For more on the $Q(n)$ and related functions and their asymptotics, see The Art of Computer Programming, Vol. 1 (3rd ed.), Section 1.2.11.3.