Here is a short argument you may find more convincing which doesn't seem to assume you know anything but basic linear algebra, the inverse function theorem, and existence/uniqueness of solutions to ODEs.
Let $M$ be a smooth vector space. The tangent space $T_0 M$ is also a vector space. The tangent space $T_0 M$ is functorial for smooth linear maps.
There is a natural transformation $\phi_M: M \to T_0 M$ given by $x \mapsto \gamma_x'(0)$, where $\gamma_x(t) = tx$, meaning that if $f: M \to N$ is a smooth linear map, we have $df_0 \phi_M = \phi_N f$. If we know that $\phi_M$ is a natural isomorphism, then we see that $f$ is invertible if and only if $df_0$ is invertible; because $df_x$ is canonically identified with $df_0$ (as $f$ is linear), we see that when $f$ is a smooth linear map which is invertible as a linear map, $f$ is also a diffeomorphism.
Let me prove that $\phi_M$ is additive; that it respects scaling is similar. That it is invertible follows because there exists a unique solution $\gamma_{v}$ to $\gamma(0) = 0$ and $\gamma'(t) = v$, where we identify $T_{\gamma(t)} M \cong T_0 M$ by translation. (This is just the statement that the exponential map exists; it is inverse to $\phi_M$.)
Lemma. If $P: M \times M \to M$ is the addition map, the map $dP_{(0,0)}$ is given by addition.
Proof. Because $P(x, 0) = x$ and $P(0, y) = y$, we have $dP_{(0,0)}(v,0) = v$ and $dP_{(0,0)}(0, w) = w$. Because $dP_{(0,0)}$ is linear, we see that it's given by adding the two coordinates.
Now $$\phi_M(P(x,y)) = \frac{d}{dt}\bigg|_{t=0} tP(x,y) = \frac{d}{dt}\bigg|_{t=0} P(tx,ty) = dP_0(\phi_M x, \phi_M y) = \phi_M x + \phi_M y.$$ That is, $\phi_M$ is additive.
Now pick a basis $(e_i)$ of $M$. The map $\Bbb R^n \to M$ given by sending $(a_i)$ to $\sum a_i e_i$ is a smooth linear isomorphism. Smoothness uses finite dimensionality and the fact that scaling and addition are smooth. By the above, $df_x$ is an isomorphism for all $x$. Therefore, $f$ is in fact a diffeomorphism. So $M$ is equivalent as a smooth vector space to the Euclidean space of the appropriate dimension.