Let $b=10$. Then for each $x \in [0,1)$, there is a unique sequence of numbers $a_1,a_2,\ldots$ in $\{0,\ldots,9\}$ not ending in an infinite sequence of $9$'s such that $$x=a_1b^{-1}+a_2b^{-2}+a_3b^{-3}+\cdots.$$
For example: $$0.83 = 8\cdot b^{-1}+3\cdot b^{-2}+0\cdot b^{-3}+\cdots$$
I'm wondering if we there's a similar theorem involving $e$, but with everything made continuous. Something like this:
Theorem. For each $x \in [0,1)$, there is a unique function $f: (0,\infty) \rightarrow [0,\infty)$ satisfying [insert deep condition here] such that $x = \int_0^\infty f(\alpha) e^{-\alpha} d\alpha$.
(This is the Laplace transform of $f$ evaluated at $1$.)
The idea is that we then proceed to define that $f$ is the "base-$e$" representation of the number $x$. It would then probably be easy to extend the idea to all of $\mathbb{R}_{>0}$, and hectic insights would hopefully follow.
What you are looking for is the concept of $\beta$-expansion. This is the same as the usual base-$b$ number systems for integer $b$, except now $\beta>1$ can be an arbitrary real number. That is, you can still write all reals as sums $$x=\sum_{k=-N}^\infty a_k\beta^{-k}$$ with each $a_j$ being an integer strictly smaller than $\beta$. So the $e$-expansion would have coefficients $a_k\in\{0,1,2\}$. In general you don't have uniqueness of the coefficients, but this is also the case in the usual decimal expansion, since $0.999\dots = 1$.
The problem with the integral formulation is that there is too much freedom. You could take for instance just the constant functions to represent all of $[0,1)$ uniquely as $$x = \int_0^\infty xe^{-\alpha}d\alpha,$$ but this wouldn't be very interesting. Or you could take any function $f:(0,\infty)\to(0,\infty)$ such that the integral diverges. Then $$\int_0^xf(\alpha)e^{-\alpha}d\alpha$$ would give any positive real for some $0\leq x<\infty$. That is the unique representation in this version would just be $f$ multiplied by the characteristic function of some interval $[0,x]$.