Hint: Use Cantor Normal Form and the fact that $\alpha\cdot(\beta+\gamma)=\alpha\cdot\beta+\alpha\cdot\gamma$ for any ordinals $\alpha,\beta,\gamma$. With this you can prove the equivalence
Edit: $(\Rightarrow)$ Let us prove by induction on $\alpha$ that if $\alpha$ is a limit ordinal, it has the prescribed form. There are two cases:
There is some $\gamma<\alpha$ such that there are no limit ordinals between $\gamma$ and $\alpha$. Let $\gamma_0$ be the greatest limit ordinal with $\gamma$ with $\gamma<\alpha$; which clearly exists in this case. We have that $\gamma_0+\omega$ is the least limit ordinal greater than $\gamma_0$, but so is $\alpha$, hence $\alpha=\gamma_0+\omega$. By the inductive hypothesis, $\gamma_0=\omega\cdot\beta'$ for some $\beta'$, thus $\alpha=\gamma_0+\omega=\omega\cdot(\beta'+1).$
For any $\gamma<\alpha$ there always exist limit ordinals between $\gamma$ and $\alpha$. In this case we get that $\alpha=\sup\{\gamma<\alpha:\gamma$ is a limit ordinal$\}$. Let $\beta=\sup\{\gamma:\omega\cdot\gamma<\alpha\}$, then by the inductive hypothesis we obtain $\alpha=\lim_{\gamma\to\beta}\omega\cdot\gamma=\omega\cdot\beta.$
$(\Leftarrow)$ Just as in Asaf's Answer.