In Milnor's book "Topology from a differential viewpoint" on page one he defines a smooth manifold to be a subset $M \subset \mathbb R^n$ which is locally diffeomorphic to some open subset of $\mathbb R^k$, i.e. every point $x \in M$ has a neighborhood $U \subset \mathbb R^n$ such that $U \cap M = V$ for some open $V \subset \mathbb R^k$ . The usual definition I know is that a smooth manifold is a (hausdorff and second countable) topological space $M$ together with an open cover $\{U_{\alpha}\}$ and homeomorphisms $f_{\alpha} : U_{\alpha} \rightarrow V_{\alpha}$ such that $V_{\alpha} \subset \mathbb R^k$ are open and the transition functions $f_{\beta}f_{\alpha}^{-1}$ are smooth (where defined).
Question: How does the usual definition of smooth manifold imply Milnor's definition of smooth manifold?
You seem to be bothered by the fact that in Milnor's definition one talks of smooth maps, whereas in the chart definition, the $f_\alpha$ are only homeomorphisms. However, once we require the transition functions to be smooth, we can actually view the $f_\alpha$ as being smooth as well.
By the implicit function theorem, a $k$-manifold smoothly embedded in Euclidean $n$-space will be the graph of a smooth vector-valued function over a suitable coordinate $k$-plane in $\mathbb{R}^n$. This implies the smoothness of the transition functions. Conversely, of you have a smooth manifold (in the sense of smooth transition functions, etc.) then Whitney gives you a smooth embedding in Euclidean space.