I'm trying to learn some Lie algebra theory with bare bones knowledge of differentiable manifolds, and little knowledge of Lie groups. I see why the exponential map $\exp: \mathfrak{g} \to G$ is surjective if $G$ is a Lie subgroup of $GL_n(\mathbf{C})$. However, my intuition is a little loose when it comes to isomorphisms of Lie groups. If $H$ is a Lie group isomorphic to some matrix Lie group, does this imply that the exponential map $\exp: \mathfrak{h} \to H$ is surjective. Furthermore, is there a nicer condition to guarantee that a Lie group is isomorphic to a matrix Lie group (it seems like almost all interesting examples of Lie groups are, except for the covering spaces of certain matrix Lie groups)?
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First, it is not true that the exponential map is surjective if $G$ is a Lie subgroup of $\operatorname{GL}_n(\mathbb{C})$. One trivial situation in which it might fail to be surjective is if $G$ is not connected as can be already seen in the zero-dimensional case. Even if $G$ is connected, the exponential map might not be onto (see this example).
However, if $G$ is compact and connected then the exponential map is onto. In this case, $G$ is also isomorphic to a matrix lie group.
