There is charge exactly at the surface of the shell, so you can't unambiguously define the E-field at that point. One reasonable convention would be to define the electric field at that point by the electric force that is exerted on the charge there. In this case it is a charge per unit area so the electric field would be defined as $E=P/\sigma$.
Since charges do not exert a force on themselves, to find the force on an infinitesimal area, the electric field of the infinitesimal area itself should be excluded. In other words, this result can be obtained by cutting a small hole out of the shell and finding the electric field due to the rest of the shell, excluding that hole.
The E-field exactly at $r=a$ found this way comes out to $E=\frac{Q}{8\pi\epsilon_0 a^2}$, or half the maximum value. The calculation is left as an exercise to the reader.
This is gives the pressure due to the electric force that is felt by the shell as
$$ P=\sigma E=\sigma\frac{Q}{8\pi\epsilon_0 a^2} = \frac{Q}{4\pi a^2}\frac{Q}{8\pi\epsilon_0 a^2}=\frac{Q^2}{32\pi^2\epsilon_0a^4}$$
which agrees with the pressure as calculated with other methods.
The more typical convention is that the electric field is simply undefined at that point. In any case, regardless of convention all the physical measurables (force, pressure, etc) are the same.