Let $M$ be a smooth manifold. Let $p \in M$ be fixed and $v_p, w_p \in T_p M$. Suppose that
$$(f_*)_p(v_p) = (f_*)(w_p)$$
for all smooth maps $f: M \to \mathbb{R}$ (here $(f_*)_p: T_pM \to T_{f(p)}\mathbb{R}\cong \mathbb{R} $ denote the differential of $f$).
Can we conclude that $v_p = w_p$.
Obviously, the answer is yes. I simply have to pick the right smooth map $f$. I think this will somehow include bump functions or something like that.
By working in a chart, it is no restriction to assume that $M$ is an open subset of $\mathbb R^n$, and then the tangent space at $p$ is naturally identified with $\mathbb R^n$. The differential at $p$ of (the restriction to $M$ of) a linear map $f : \mathbb R^n \to \mathbb R$ is just $f$ itself.
So we have that $v_p, w_p \in \mathbb R^n$ are such that $f(v_p) = f(w_p)$ for every linear map $f : \mathbb R^n \to \mathbb R$. Hence $v_p = w_p$.