Let $(-A)$ be a real Hurwitz lower-triangular matrix (this implies that all the eigenvalues of $A$ are real and negative). Since $(-A)$ is Hurwitz, we know that there exist $\alpha,\lambda>0$ such that
$$ ||e^{-At}|| \le \alpha e^{-\lambda t} $$
for all $t\ge0$. Is it possible to choose the pair $(\alpha,\lambda)$ so that $\lambda$ is equal to the smallest eigenvalue of $A$? If so, how much is the smallest corresponding $\alpha$?
Remark. From this question and the answers therein, it seems that when $(-A)$ is just Hurwitz, it is not possible to choose $\lambda$ equal to the smallest eigenvalue of $A$. But now I am introducing the further property that $A$ is lower triangular.
The answer to your first question is negative. The Jordan canonical form is a triangular matrix, right? That's why nothing changes.
So in general there is no best possible constant but you can take it as close as desired to the smallest eigenvalue.