The direct meaning of 'natural isomorphism' in this case is that for each vector space V, you have an isomorphism \phi_V : V \to V^{**}, and furthermore, for every linear transformation T : V \to W, you have the identity \phi_W(T(v)) = T^{**}(\phi_V(v)).
(T^{**} is the corresponding action of T on the double-dual)
If you're comfortable with depicting linear tranformations as diagrams, you have
<br />
\begin{array}{rcl}<br />
V &\xrightarrow{\phi_V}& V^{**} \\<br />
T \downarrow & & \downarrow T^{**} \\<br />
W &\xrightarrow{\phi_W}& W^{**}<br />
The practical effect is that the naturality condition of a transformation ensures that you generally don't have to worry about when it applies, since you can do (certain) things in any order you please.
Compare with linear transformations on vector spaces; the linear transformation "commutes" with addition and scalar multiplication, so if you wanted to compute something like T(rv + w), you can either do the operations first then apply T, or apply T then do the operations, or some combination of the two.
In fact, a natural transformation is defined as a homomorphism of "constructions". (More precisely, of functors) In this case, it is to the "double dual" functor from the the "identity" construction that leaves a vector space / linear transformation unchanged.
If you're familiar with homotopies, natural isomorphisms are related. (Both in a superficial and in a meaningful sense)
Sometimes, though, natural is really just used in the plain-English sense. Many common examples of natural isomorphisms in the technical sense turn out to be natural in the plain-English sense too. (like the double dual)