Is it because of the division of the whole term by $e^z$? So, it would not be allowed to write $=$?
$\displaystyle \frac{1}{1 + 2^{-1}} = \frac{1}{1 + 0.5} = \frac{1}{1.5}$ has to be written with $=$, but it may not be written with $\equiv$. Correct?
In the second example, it is just a mathematical transformation without dividing the whole thing by something. In the first example, however, this seems to be different.
$\displaystyle p(z) = \frac{e^z}{1 + e^z} \equiv \frac{1}{1 + e^{-z}}$ shall represent a logistic function.
The context of everything is empirical research in economics.