EDIT: Question 1 has been settled (below). The bounty is for question 2.
Let $n\geq 3$ and consider the following function $f:S_n\backslash\{e\}\rightarrow \mathbb{R}$
$$f(\sigma)=\sum_{i=1}^n\frac{1}{\sqrt{n^{i+\sigma(i)}}}$$
where $\sigma\in S_n$ is considered a function $\sigma:\{1,\dots,n\}\rightarrow \{1,\dots,n\}.$
I believe $f$ is maximised at $\sigma=(n-1\quad n)$ where it takes on the value
$$f(\sigma)=\frac{1}{n^{3n-1}}\frac{n^n-1}{n-1}.$$
- Prove this assertion.
Secondly I am interested in upper-bounding the sum for $k\in \mathbb{N}$:
$$\frac{1}{4n^{2k(n-2)}}\sum_{\sigma\in S_n\backslash{e}}f(\sigma)^{2k},$$
particularly in the asymptotic case $n\rightarrow \infty$ and $k=k(n)\rightarrow \infty$.
- Any bounds that are "significantly" better than using the trivial $$\sum_{j=1}^N|a_j|\leq N\cdot \max_j|a_j|.$$
Context:
These sums are related to bounding the distance to random of the random walk on the quantum group $\widehat{S_n}$ (given by $F(\widehat{S_n})=\mathbb{C}S_n$) driven by a state (positive definite function on $G$) $u\in M_p(\widehat{S_n})$ given by the permutation representation together with the unit vector $\alpha=(\alpha_i)$ where $$\alpha_i=\sqrt{n^{n-i}\frac{n-1}{n^n-1}}.$$
Regarding question 2, one can improve on the trivial bound a bit, but I'm not sure this counts as "significant".
Let $f_0 = \max_{\sigma \neq e} f(\sigma)$. As you noted, $\frac{n! - 1}{4n^{2k(n-2)}} f_0^{2k}$ is a trivial upper bound. For the sake of later comparison, let us call this trivial bound $M_0$.
Now observe that $f_0 \approx \frac{1}{n}$. Moreover, $f(\sigma) \approx \frac{1}{n}$ if and only if $\sigma(1) = 1$, and $f(\sigma) = O \left( n^{-\frac32} \right)$ otherwise (this order of magnitude is attained if either $\sigma(1) = 2$ or $\sigma(2) = 1$).
That is to say, only $(n-1)! - 1$ non-identity permutations come close to the maximum value, and for the remaining permutations, $f(\sigma)$ is smaller by a factor of $n^{\frac12}$. Using the trivial bound on these two sets of permutations separately, we have $$ \frac{1}{4n^{2k(n-2)}} \sum_{\sigma \in S_n \setminus \{e \}} f(\sigma)^{2k} \lessapprox \frac{(n-1)!-1}{4n^{2k(n-2)}} f_0^{2k} + \frac{n! - (n-1)!}{4n^{2k(n-2)}} \left( f_0 n^{-\frac12} \right)^{2k} \sim \left( n^{-1} + n^{-k} \right) M_0.$$
Hence this new upper bound is only a factor $n$ smaller than the trivial one. However, we cannot hope to do much better*: $$ \frac{1}{4n^{2k(n-2)}} \sum_{\sigma \in S_n \setminus \{e \}} f(\sigma)^{2k} \ge \frac{1}{4n^{2k(n-2)}} \sum_{\substack{\sigma \in S_n \setminus \{ e \} \\ \sigma(1) = 1}} f(\sigma)^{2k} \ge \frac{(n-1)! - 1}{4n^{2k(n-2)}} \cdot \frac{1}{n^{2k}} \gtrapprox \frac{(n-1)! - 1}{4n^{2k(n-2)}} f_0^{2k} \sim \frac{1}{n} M_0.$$
[*The approximation in the second line (the $\gtrapprox$) is only valid when $k$ does not grow too quickly with $n$. $f_0 = \frac{1}{n} + O(n^{-2})$, and if $k$ is linear in $n$, then $f_0^{2k}$ can be much larger than $\frac{1}{n^{2k}}$.]
I've used asymptotic approximations here just to avoid having to be too careful and fiddling around with constants. However, it shouldn't be too hard to turn these into bona fide bounds: $f_0$ is essentially a rapidly converging geometric series.