As you said, assuming you take $b=a+ker(\pi_\psi)\in A/ker(\pi_\psi)$ such that $\tau(b)=0$, then
$0 = \tau(bb^*) = \tau(b^*b)=\psi(a^*a) =\langle\pi_{\psi}(a^*a)e_{\psi},e_{\psi}\rangle=\langle\pi_{\psi}(a)\pi_\psi(a)^*e_{\psi},e_{\psi}\rangle=\langle\pi_\psi(a)^*e_\psi,\pi_\psi(a)^*e_\psi\rangle$, so $\pi_\psi(a)^*e_\psi = 0$, using the symmetry of the trace and the fact that $\pi_\psi$ is a *-morphism. I claim that $a\in ker_(\pi)$ automatically follows.
Indeed, you want to show that $\pi_\psi(a)\pi(A)e_\psi = 0$, and it will imply (because $e_\psi$ is cyclic for $\pi$) that $\pi_\psi(a)H_\pi = 0$, hence $\pi_\psi(a)=0$, so $a\in ker(\pi_\psi)$, hence $b=0$.
But this is immediate, since $\vert\vert\pi_\psi(a)\pi(c)e_\psi\vert\vert^2=\langle\pi_\psi(a)\pi_\psi(c)e_\psi,\pi_\psi(a)\pi_\psi(c)e_\psi\rangle=\langle\pi_\psi(c^*a^*ac)e_\psi,e_\psi\rangle = \psi((c^*a^*)(ac))=\psi((ac)(c^*a^*))=\langle\pi_\psi(a)\pi_\psi(c)\pi_\psi(c^*)\pi_\psi(a^*)e_\psi,e_\psi\rangle = 0$.