This sounds like it could be written down somewhereconjecture is proven in the literature on Hilbert's third problem. I believe I can sketch a proof.
Let $X$ be a space (which will be $\mathbb R^n$ for us), and $G$ a group of isometries of $X$theorem 7. We define $\mathcal P(X,G)$ to be the $G$-scissor congruence group3 of $X$. It is defined as a subgroup of the free abelian group generated"Incidence matrices, geometrical bases, combinatorial prebases and matroids" by polytopes in $X$, modulo the following relations.
$\tag{1} P=\sqcup P_i \implies [P]=\sum [P_i]$
$\tag{2} [P]=[gP], \forall g\in G$
So two polytopes are equivalent if they can be decomposed into pieces which are equivalent modulo $G$T. When $G=\lbrace 0\rbrace$ let's call this group $\tilde{\mathcal P}(X)$V. Apparently it was a fact known to JessenAlekseyevskaya and Thorup, that the relations in $\tilde{\mathcal P}(X)$ are generated by relations of the form you describe (different triangulations are equal). One reference I found is.M. Gelfand. See also theorem 24.102 in "Scissor congruences, group homology and characteristic classes" by Dupont (there it"Bases in Systems of Simplices and Chambers" by Alekseyevskaya where the same result is phrased as $\tilde{\mathcal P}(X)$ being isomorphic to a certain homology group)proved.
NowA previous version of this answer described the similar situation with scissor congruence groups, but I'm no longer certain that one can get a proof of your conjectureusing such theorems anymore. It is worth mentioning here that a relation in $K(S)$ comes from volume forms and can be written as
$$\sum \alpha_i \chi_{\Delta_i}\text{dVol}=\sum \beta_i \chi_{\Delta_i}\text{dVol}$$
and this implies
$$\sum\alpha_i \Delta_i =\sum \beta_i \Delta_i$$
in $\tilde{\mathcal P}(X)$ so this relationthere is a combination of identitiesvery similar theorem of Pachner which says that come from triangulationstwo PL-homeomorphic triangulated PL-manifolds are related by a sequence of the convex hull on $n+2$ points from the theorem above. Now, because all the polytopes involved have vertices in $S$"bistellar flips", the only triangulations involvedwhich are essentially the ones with verticesgenerating relations in $S$your conjecture. We conclude that $K(S)$ is generated by identities on simplices as inI suspect there should be a proof of your conjecture using Pachner's theorem, but I haven't given it much thought.