Let me first give a much more intuitive argument for why a finite Boolean rng is a ring, and then relate it to Stone's construction. Any Boolean rng is in particular a lattice (bounded below but not necessarily above), with the lattice operations defined by $$x\wedge y=xy$$ and $$x\vee y=x+y+xy.$$ Since multiplication is the same as the lattice join operation, a multiplicative identity is the same thing as a greatest element of the lattice. But now the conclusion is obvious: in a finite lattice, you can find a greatest element by just taking the join of all the elements.
Now where does Stone's construction come in? It turns out that if you translate an $n$-fold join back into the rng operations, you just get the sum of the elementary symmetric polynomials. This is clear for $n=2$ from the definition: $$x\vee y=(x+y)+xy=e_1(x,y)+e_2(x,y).$$ If you calculate out what you get for $n=3$, it is not hard to guess that it works for any $n$, and then it's also not hard to prove it by induction on $n$.
This is also closely related to inclusion-exclusion (which is another way you could come up with it): to count each element of an $n$-fold union $x_1\cup\dots \cup x_n$ exactly once, inclusion-exclusion tells you to first count each element of each of $x_1,x_2,\dots,x_n$ once, then subtract each element of each binary intersection, then add in each element of each ternary intersection, and so on. In other words, if you let $1_x$ denote the characteristic function of a set $x$, then the equation $$1_{x_1\cup\dots \cup x_n}=e_1(1_{x_1},\dots,1_{x_n})-e_2(1_{x_1},\dots,1_{x_n})+\dots+(-1)^{n-1}e_n(1_{x_1},\dots,1_{x_n})$$ is true (say, in the ring of all integer-valued functions on your universal set). Taking this mod $2$ so you are working with $\mathbb{F}_2$-valued functions which you can identify with the power set Boolean ring, this says exactly that $$x_1\vee\dots\vee x_n=e_1(x_1,\dots,x_n)+e_2(x_1,\dots,x_n)+\dots+e_n(x_1,\dots,x_n).$$
(Of course, this does not prove that this identity is true in an abstract Boolean rng unless you already have something like the representation theorem, but it's a way you might come up with it as a guess.)
Yet another way you can come up with this formula: the join operation is just what you get by conjugating the meet operation by the complement operation (of course this only makes sense when you have a unit). In terms of ring operations, the complement operation is $x\mapsto 1+x$, so this says that $x_1\vee \dots \vee x_n$ should be given by $$1+(1+x_1)(1+x_2)\dots(1+x_n).$$ When you expand out that product you'll just get the sum of all possible products of some of the $x_i$'s, and then when you add $1$ you'll remove the empty product so you're just left with the sum of the elementary symmetric polynomials. (If you use the same idea but with integer-valued functions where the complementation operation is $x\mapsto 1-x$, this gives a slick proof of inclusion-exclusion.)