Suppose I want to prove that, for some sentence $\phi$, $Con(ZFC) \to Con(ZFC + \phi)$. And to do this, I prove that for some classe $C = \{ x : \psi(x)\}$, $C \vDash ZFC$ and $C \vDash \phi$ - using the concept of relativization of formulas. Is this enough to prove the desired result?
I thought it would go along those lines: Supose $(\mathbf{M}, E)$ is a model for ZFC and consider the set $\mathbf{N} = \{ a \in \mathbf{M} : M \vDash \psi(a) \} \subseteq \mathbf{M} $. Does the relativization argument prove that $(\mathbf{N}, E)$ is a model of $ZFC + \phi$?
Yes, that's correct. Note that strictly speaking, you can't prove (or even state) something like $C \vDash ZFC$, since $ZFC$ has infinitely many axioms and you can only relativize one of them at a time. What you can prove is a metatheorem which says that for each individual axiom $\psi$ of $ZFC$, $C\vDash\psi$ is a theorem of $ZFC$. This is then enough to conclude that $(\mathbf{N},E)\vDash ZFC$, by interpreting each of these theorems $C\vDash\psi$ in the model $(\mathbf{M},E)$.