Your use of the term "truth assignments" indicates that you are asking this question in the context of propositional logic, rather than the context of model theory and first order logic, where it often arises.
The answer is: Yes, there are $K$ for which $K\neq \operatorname{Mod}(\operatorname{Th}(K))$.
In the propositional logic context, we have a collection $K$ of truth assignments of a fixed set of propositional variables to {true,false}. That is, $K$ is a set of rows in the truth table. In this case, $\operatorname{Th}(K)$ is the set of propositional assertions true in all those rows, and $\operatorname{Mod}(\operatorname{Th}(K))$ is the set of all models of all those assertions. Since the rows appearing in $K$ do model all those assertions, we see that immediately that $K\subset \operatorname{Mod}(\operatorname{Th}(K))$.
But here is a counterexample showing that $K\neq \operatorname{Mod}(\operatorname{Th}(K))$ is possible. Suppose that there are infinitely many propositional variables $p_0,p_1,\ldots$, and let $K$ be the rows for which at most finitely many $p_n$ are true. In this case, I claim $K\neq \operatorname{Mod}(\operatorname{Th}(K))$. The reason is that any statement $\varphi$ involves only finitely many variables, and so if it is not tautological, that is, if it fails anywhere, then it will fail in a model for which only finitely many variables are true (just ignore all variables not in $\varphi$). Thus, $\operatorname{Th}(K)$ includes only the tautologies, and so $\operatorname{Mod}(\operatorname{Th}(K))$ includes all truth assignments. So this is a counterexample.
It is not difficult to see that any counterexample will involve infinitely many propositional variables, since if there are only finitely many variables, then the assingments in $K$ can be explicitly described and the theory axiomatized.
In the context of first order logic, we take $K$ to be a set of first order structures, and there are numerous examples of $K$ not forming an elementary class, as in the link provided by Asaf. One example is the collection $K$ of all countably infinite structures (of a fixed consistent theory in a countable language). This will not be $\operatorname{Mod}(\operatorname{Th}(K))$, since by Lowenheim-Skolem, there are arbitrary large structures of any consistent theory.