The non-modal definition of valuation π is a mapping from propositional letters (e.g. p, q, r) to truth-values (e.g. elements of Bool = {⊤, ⊥}):
Alethic valuation function. π : Prop → Bool.
π(p) is an assignment of a truth-value to the propositional letter p. The modal definition of valuation V that you mentioned is a mapping from propositional letters not to truth-values, but to subsets of W:
Modal valuation function 1. V1 : Prop → ρ(W).
V1(p) is not an assignment of a truth-value to p because the truth-value of p depends on the world it's evaluated at. V1(p) is an assignment to p of that subset of W which includes those worlds that satisfy p.
It is, however, possible to think of V as a mapping from pairs (p, w) ∈ Prop × W to truth-values:
Modal valuation function 2. V2 : Prop × W → Bool.
Here V2(p, w) is no longer unary and takes a proposition and a world and gives a truth-value. Now instead of w ∈ V1(p) we would say the equivalent V2(p, w) = ⊤.
For contrast, let's consider the Tarski truth-conditions of propositional letter p in those three contexts:
(Alethic) M |= p iff π(p) = ⊤.
(Modal1) M, w |= p iff w ∈ V1(p).
(Modal2) M, w |= p iff V2(p, w) = ⊤.