Edit: Below I assume that "measure" means "positive measure". Looking back at the question, it seems you are probably talking about real measures. The result for real measures follows, since any real measure is the difference of two finite positive measures.
If I'm not mistaken the answer to the question is yes (at least for finite $\mu$; recall that Radon measures are finite):
Suppose $\mu$ is a finite regular Borel measure on $[0,\omega_1]$. There exist $\alpha<\omega_1$, $a_j\ge 0$ for $0\le j\le\alpha$ and $c\ge0$ such that $\mu=\sum_{j\le\alpha}a_j\delta_j+c\delta_{\omega_1}$.
Proof: Let $E=\{j\in[0,\omega_1]:\mu(\{j\})>0\}$. Countable additivity shows that $E$ is countable. So there exists $\alpha<\omega_1$ with $$E\subset[0,\alpha]\cup\{\omega_1\}.$$Define $a_j=\mu(\{j\})$ for $j\le\alpha$ and $c=\mu(\{\omega_1\})$, and let $$\mu_1=\sum_{j\le\alpha}a_j\delta_j+c\delta_{\omega_1},$$ $$\nu=\mu-\mu_1.$$We need to show $\nu=0$. Note first that $\mu_1\le\mu$ (because $\mu_1(A)=\mu(A\cap E)$ [hint: $A\cap E$ is countable]), so $\nu\ge0$; hence it's enough to show that $\nu([0,\omega_1])=0$.
But $\nu(\{j\})=0$ for every $j\in[0,\omega_1]$, so countable additivity shows that$$\nu([0,\alpha])=0\quad(\alpha<\omega_1).$$If $K$ is a compact subset of $[0,\omega_1)$ there exists $\alpha<\omega_1$ with $K\subset[0,\alpha)$; hence $$\nu(K)=0\quad(\text{compact } K\subset[0,\omega_1)).$$So regularity shows that $\nu([0,\omega_1))=0$, and since $\nu(\{\omega_1\})=0$ we have $\nu([0,\omega_1])=0$.
Note. This is closely related to the result of Rao & Rao mentioned in the question. Indeed, we could have used Rao & Rao to obtain $\mu_1$ and $\nu$ above (I didn't do that because the construction is very simple a priori, and the version of Rao & Rao in the original version of the question was obviously false.) And in fact the result above suffices to reduce Rao & Rao to a special case:
Say $\mu$ is a (finite positive) Borel measure on $[0,\omega_1]$. Define $\mu_1$ and $\nu$ as above. Then $\mu_1$ is concentrated on a countable set, so we "only" have to show that $\nu$ is a multiple of the Dieudonne measure. So Rao & Rao is equivalent to this:
Lemma (Rao & Rao). If $\nu$ is a Borel probability measure on $[0,\omega_1]$ and $\nu(\{j\})=0$ for every $j\in[0,\omega_1]$ then $\nu$ is the Dieudonne measure.
I'm totally stuck on that, in fact it seems implausible. Edit: There's a proof here.