This is not an answer but a conjecture. It based on a first examples examples calculated by Mathematica.
$$S(a)=\frac1{a+1}-\sum_{i=1}^a\frac{\psi(-\alpha_i)}{f_a'(\alpha_i)},$$
where $f_0(x)=1$, $f_1(x)=x+3$, $f_2(x)=x^2+5x+7$,...
$$f_{n+1}(x)=(x+2)f_n(x)+1\qquad(n\ge 0),$$
(see [A193844][1]) and $\alpha_i$ are the roots of $f_a$.


  [1]: http://oeis.org/A193844