We study the algebraic symplectic geometry of multiplicative quiver varieties, which are moduli spaces of representations of certain quiver algebras, introduced by Crawley-Boevey and Shaw, called multiplicative preprojective algebras. They are multiplicative analogues of Nakajima quiver varieties. They include character varieties of (open) Riemann surfaces fixing conjugacy class closures of the monodromies around punctures, when the quiver is crab-shaped. We prove that, under suitable hypotheses on the dimension vector of the representations, or the conjugacy classes of monodromies in the character variety case, the normalisations of such moduli spaces are symplectic singularities and that the existence of a symplectic resolution depends on a combinatorial condition on the quiver and the dimension vector. These results are analogous to those obtained by Bellamy and the first author in the ordinary quiver variety case, and for character varieties of closed Riemann surfaces. At the end of the paper, we outline some conjectural generalisations to moduli spaces of objects in 2-Calabi--Yau categories.