Let $M$ a manifold. Two atlas $A_1=\{(U_i,\varphi_i)\}$ and $A_2=\{(V_i,\psi_i)\}$. They define the same smooth structure if whenever $f$ is smooth wrt $A_1$ then it will be smooth wrt $A_2$. For example $$A_1=\{(\mathbb R^n,id_{\mathbb R^n})\}$$ and $$A_2=\{(B_1(x),Id_{B_1(x)})\mid x\in \mathbb R^n\}$$ are two different atlas but they define the same smooth structure.
Do you have an example (on $\mathbb R^n$ or any easy smooth manifold) that describe two different smooth structure ? I don't really see it.