I completely agree with Siong Thye Goh's answer and consider his answer more elegant than the one I am about to present. My answer is intended to show the much more pedestrian and inelegant but still viable approach of induction.
Assume that the conjecture is true for $i$, where
$0 \leq i \leq p^s - 2.$
Then $\;\binom{p^s - 1}{i + 1},\;$ which is an integer, equals
$\;\binom{p^s - 1}{i} \times \frac{p^s - [i+1]}{i + 1}.$
By inductive assumption, $\;\binom{p^s - 1}{i} \;\equiv (-1)^i \pmod{p}.$
Further, $\;(-1)^i [-(i+1)] \equiv (i+1)(-1)^{(i+1)} \pmod{p}
\;\Rightarrow$
$\;\binom{p^s - 1}{i} \times [p^s - (i+1)]
\;\equiv\; (i + 1) (-1)^{(i+1)}\pmod{p} \;\Rightarrow$
$\;\binom{p^s - 1}{i} \times \frac{p^s - [i+1]}{i + 1}
\;\equiv\; (-1)^{(i+1)}\pmod{p}.$
$\underline{\text{Addendum}}$
As Karl indicated in his comment below, I must examine the case of
$\;(i+1) \;\equiv\; 0 \pmod{p}\;$ separately. I am working on it and will update my answer if and when I find a remedy.
Convoluted remedy found : proof by contradiction.
Let $pk$ denote the smallest multiple of $p$ such that the conjecture is false.
Then, from the induction used in the first part of this answer, the conjecture is true for $i = (pk - 1).$
Let $v_p(n) \;\equiv\;$ the largest exponent $\theta$ such that
$p^{\theta} | n.$
Let $v_p[(p^s - 1)!] = \alpha, \;v_p[(pk - 1)!] = \beta,
\;v_p[(p^s - pk)!] = \gamma,\;$ and $\;v_p(pk) = \delta.$
By assumption, $\;\binom{p^s - 1}{pk-1} \;\equiv\; (-1)^{(pk-1)}
\;\pmod{p}.$
Therefore, $\;\alpha = \beta + \gamma,\;
(p^s - 1)!\;$ has form $\;(p^\alpha) \times a,$
$(pk-1)!(p^s - pk)!\;$ has form $\;(p^\alpha) \times b,$
where $p$ does not divide $a$ or $b$ and
$a \equiv b\times (-1)^{(pk-1)} \pmod{p}.$
$v_p(pk) = \delta \;\Rightarrow v_p(p^s - pk) = \delta.$
Further, $\;pk = p^\delta \times r,\;$ where
$p$ does not divide $r \;\Rightarrow\;$
$(p^s - pk)\;$ will have form $(p^\delta) \times (-t),\;$
where $\;t \;\equiv\; r \pmod{p}.$
Thus, $\;(pk)!(p^s - 1 - pk)! \;=\; $
$(pk) \times [(pk-1)!]\times\frac{(p^s - pk)!}{(p^s - pk)},$
which can be re-expressed as $(p^\delta \times r) \times (p^\alpha \times b)$
$\frac{1}{p^\delta\times(-t)} \;\Rightarrow\;$
$\binom{p^s - 1}{pk} \;\equiv\; (-1)^{(pk-1)} \times \frac{-t}{r}
\;\equiv\; (-1)^{(pk)} \pmod{p}.$
This yields a contradiction. Therefore, the conjecture also holds for any $i < p^s - 1,$
where $i$ is a multiple of $p$.