First notice that $k e^x $ is equal to $k$ when $x=0$ so it doesn't satisfy $f(0)=1$ when $k \neq 1$. The property $f' = f$ assures you that $f$ is a multiple of $e^x$ and the value of $f$ at $0$ enables you to say which multiple of $e^x$ $f$ is. Here's a proof of that :
If there is another differentiable function $f$ such that $f'(x) = f(x)$ and $f(0) = 1$ then since $e^x \neq 0$ for all $x$ we have
$$ \frac{d}{dx}\frac{f(x)}{e^x} = \frac{f'(x)e^x - (e^x)'f}{e^x} = \frac{f(x)e^x-f(x)e^x}{e^x} = 0.$$
This means that $\frac{f(x)}{e^x}$ is constant and $f(x) = k e^x$ for some $k \in \mathbb R$.
Plugging in $x = 0$ we get
$$ f(0) = k$$
and $f(x) = f(0)e^x = e^x$.
Therefore any other value than $1$ for $f(0)$ would give another different multiple of $e^x.$
Edit:
To prove that $e^x$ is the unique function such that $f' = f$ and $f(0) = 1$ one must of course first show that $(e^x)' = e^x$ and $e^0 = 1$. In the proof above I assume this therefore this proof only shows that if $f' = f, f(0) = 1$ has a solution then it is is unique (you can see this by replacing $e^x$ by $g(x)$ in the proof).
Proving that $e^x$ is a solution of $f' = f,f(0) = 1$ depends heavily on how you define $e^x.$
Using the Picard-Lindelöf theorem one can easily show that $f' =f, f(0)=1$ has a unique (maximal) solution. Define $e^x$ as this unique solution and then by definition $e^x$ is the only function such that $f'=f, f(0) =1.$ Obviously this isn't very insightful since you still want to be sure that this $e^x$ is the one you know as $ \sum_k \frac{x^k}{k!}$ or $\lim_{n \to \infty}(1 + x/n)^n.$
This all comes down to showing that $(e^x)' = e^x,e^0 =1$ with your preferred definition of $e^x.$ You can find this proof here on the website (Derivative of exponential function proof). I'm sure you can find a few other proofs here by using the search functionality.