Using Theorem 4.1 from Non-measurable sets (hosted on joelshapiro.org) by Joel H. Shapiro, we can find such a decomposition of any set of positive measure.
In that article, Shapiro gave a non-measurable subset $\mathit{NM}$ of $[0,1)$ such that any measurable subset of it has measure $0$, and any measurable superset ($\subseteq[0,1)$) of it has measure $1$. Its complement in $[0,1)$, $\mathit{NM}' = [0,1) \setminus \mathit{NM},$ has the same properties; specifically, any measurable subset of it has measure $0$. They already constitute a desired decomposition of $[0,1)$. We can use these two sets to decompose any subset of $\mathbb{R}$ of positive measure.
Let $A, B \subseteq \mathbb{R}$ be
$$A = \mathit{NM} + \mathbb{Z} = \bigcup_{n \in \mathbb{Z}} (\mathit{NM}+n),\quad\text{and}\quad B = \mathit{NM'} + \mathbb{Z}.$$
We have $A \cup B = \mathbb{R}$ and $A \cap B = \emptyset$. More importantly, they both have inner measure $0$. Let $E$ be a measurable subset of $A$.
$$\begin{split}
\mu(E)&=\mu\left(\bigcup_{n\in\mathbb{Z}}E\cap[n,n+1)\right)\\
&=\sum_{n\in\mathbb{Z}}\mu(E\cap[n,n+1))\\
&=\sum_{n\in\mathbb{Z}}\mu(\underbrace{(E-n)\cap[0,1)}_{\subseteq\mathit{NM}})\\
&=\sum_{n\in\mathbb{Z}}0=0.
\end{split}$$
Similarly, we can show $B$ has inner measure $0$. Now, given any subset $X$ of $\mathbb{R}$ of positive measure, we can simply decompose it into its intersections with $A$ and $B$, i.e. $X \cap A$ and $X \cap B$. $\square$