$\newcommand{\d}{\,\mathrm{d}}\newcommand{\P}{\mathscr{P}}$A bounded function $f:[a,b]\to\Bbb R$ is Riemann integrable if and only if (various equivalent definitions, Spivak's is equivalent to this one) there exists $J\in\Bbb R$ such that for all $\epsilon>0$ there exists $\delta>0$ such that for all tagged partitions $\P$ of $[a,b]$ with mesh less than $\delta$, we have: $$\left|\sum_{(x,y,t)\in\mathscr{P}}(y-x)f(t)-J\right|<\epsilon$$
In which case, we define: $$\int_a^bf:=J$$
In particular, we know $x\mapsto e^x$ is Riemann integrable on $[0,1]$. Consider the tagged partitions $\P_n$ which have elements $((k-1)/n,k/n,k/n)$ for $1\le k\le n$. I know that for all $\epsilon>0$ there is $\delta>0$ such that, if the mesh $\|\P_n\|=1/n$ is less then $\delta$, then: $$\tag{$\ast$}\int_0^1e^x\d x-\epsilon<\frac{1}{n}\sum_{k=1}^ne^{k/n}=\sum_{(x,y,t)\in\P_n}(y-x)e^t<\int_0^1e^x\d x+\epsilon$$
But of course, if $N:=\lceil\delta^{-1}\rceil+1$ then for all $n\ge N$ we have $(\ast)$ since $1/n<\delta$. By definition of the limit of a sequence indexed in $\Bbb N$, it follows that: $$\lim_{n\to\infty}\frac{1}{n}\sum_{k=1}^ne^{k/n}=\int_a^b e^x\d x$$
How can we relate that to the Darboux concept of $U$ and $L$? A full proof is in the Wikipedia page. But I'll sketch the idea. As you observe, we have: $$\frac{1}{n}\sum_{k=1}^ne^{k/n}=U(f;\P_n)$$With $f:x\mapsto e^x$ defined on $[0,1]$. I know: $$\inf_{\P}U(f;\P)=\int_0^1e^x\d x$$
But notice that if $\P$ is a refinement of $\P'$, then $U(f;\P)\le U(f;\P')$. Moreover, the $\inf$ of a set of real numbers can be attained as a sequence $a_1\ge a_2\ge\cdots$ tending to the $\inf$. You can imagine taking, for large $n$, those special $\P=a_n$ which have $U(f;\P)$ being close to $\int_0^1 e^x\d x$. But for very large $n$ it is true that $U(f;\P)\approx U(f;\P_n)$ since the $0,1/n,2/n,\cdots$ partition has sufficiently fine divisions. So you can obtain $U(f;\P_n)\to\int_0^1e^x\d x$.