Your definition is essentially fine, but incomplete.
You need to indicate that the union you are taking is disjoint, and also need a clause stating that if $A$ is a measurable subset of an interval $I$, then the measure of the complement of $A$ in $I$ is the measure of $I$ minus that of $A$. Once you add this clause your "naive" definition indeed provides the right measure for all Borel sets. The recursion takes $\omega_1$ steps, meaning that if $\alpha$ is a (possibly infinite, but) countable ordinal, then running your definition for only $\alpha$ many stages will fail to assign measure to some Borel sets.
To be precise: We can call $A$ a level $0$ set iff it is an interval, for $\alpha$ countable, call $A$ a level $\alpha+1$ set iff it is not a level $\alpha$ set, but it is the countable union of sets $A_n$ of level $\alpha$ or the complement of a level $\alpha$ set, and call $A$ a level $\gamma$ set, for $\gamma$ a countable limit ordinal, iff it is not a level $\beta$ set for any $\beta<\gamma$, and there is a sequence $\gamma_n$ of ordinals smaller than $\gamma$, and for each $n$ there is a set $A_n$ of level $\gamma_n$, with $A=\bigcup_n A_n$. Our definition assigns measures to all sets of level $\alpha$, for any countable $\alpha$, and for each $\alpha$ there is at least one set of level $\alpha$, so we cannot stop before that stage. On the other hand, the collection of all sets of countable level is closed under the clauses of your definition.
(In descriptive set theory we actually use something very close to your approach to describe the Borel complexity of a set. This approach, of assigning a level of complexity to sets, allows us to prove statements about Borel sets by transfinite induction, and is indeed very useful. In practice, however, it is quite rare to happen upon a Borel set whose level is beyond, say, $5$.)
To see the need for the extra clause regarding complements: We want singletons to be measure zero. This is perhaps fine if we are liberal with our interpretation of the word "interval". But without the extra clause, not even the Cantor set gets assigned a measure.
Additional clauses will be needed if you want to reach all Lebesgue measurable sets. Perhaps the simplest is to say that if $A$ is measurable and has measure zero, then any subset of $A$ is also measurable with measure zero, and that if $A$ is measurable and $B$ has measure zero, then $A\cup B$ is measurable and has the same measure as $A$.
Of course, there are difficulties with this approach. For instance, one needs to verify that it is self-consistent, meaning that if a set $A$ is witnessed to be of level $\alpha$ in two different ways, we need to prove that the two "witnesses" assign to $A$ the same measure. Similarly for the additional clause I mentioned in the paragraph above. One also needs to verify that this approach captures all measurable sets. (I did not require that the unions verifying a set is level $\alpha$ be disjoint, although I required this when it came to assigning measures. Some additional care is needed to deal with this detail.)