It seems to me that you do not use the phrase natural isomorphism in the sense of category theory (as one expects when one reads the title), but in a more motivational sense:
The definition of $T : V \to V^{**}$ looks so obvious and compelling - so natural - that one should expect that $T^{-1}$ also has such a nice description.
In my opinion this is a fallacy. In fact, $T$ is defined for each (finite or infinite dimensional) vector space $V$ and one can show that it is always injective. For a general $V$ the proof requires the axiom of choice (for each $x \in V, x \ne 0$, you have to find a linear map $u \in V^*$ such that $u(x) \ne 0$), but let us ignore that here. The main issue is that $T$ is an isomorphism only for finite dimensional $V$. To prove surjectivity you must invoke at some point that $V$ has a finite basis.
That is, although $T$ is an isomorphism for finite dimensional $V$, you need to pick a basis to prove it. Viewed in this light it is not surprising that you need a basis of $V$ to describe $T^{-1}$.
Update:
You correctly observe that there is an asymmetry between the "easiness" to define of $T$ and the "trouble" to describe $T^{-1}$. As we have seen, this is due to the the fact that it easy to define $T$, but non-trivial to prove that it is an isomorphism (which is true only for finite dimensional $V$ and has a serious impact on finding the inverse).
Does this have any significance in linear algebra or other branches of mathematics? In this particular case I do not think so. But this is a somewhat "philosophical question" which I would reformulate as follows:
If we consider bijections $f : A \to B$ (we shall not be specific; $A,B$ may be sets, groups or vector spaces or something else, and $f$ may be a function or a homomorphism), can we always easily determine their inverses $f^{-1}$?
Of course, the interpretation of easy will depend on the context.
No, neither on a generic level (as for $T : V \to V^{**}$) nor on a concrete level as e.g. for one-way functions. Quotation from Wikipedia:
A one-way function is a function that is easy to compute on every input, but hard to invert given the image of a random input.
Such are used for example in the RSA cryptosystem: It is easy to encrypt a message, but very hard to decrypt the result - unless you have access to secret information.
Remark:
Martin Brandenburg has proved in his answer that there does not exist a non-zero natural transformation from the bidual functor $B$ to the identity functor on the category $\mathbf{Vect}$ of vector spaces over a field $K$. Actually his proof shows that for no full subcategory $\mathbf{Vect'} \subset \mathbf{Vect}$ containg $K$ and an infinite dimensional $V$ there exists a non-zero natural transformation from $B' = B \mid_{\mathbf{Vect'}}$ to the inclusion functor $\mathbf{Vect'} \to \mathbf{Vect}$. Therefore the best possible positive result is available on the category $\mathbf{Vect}_{fin}$ of finite dimensional vector spaces over $K$: The inverse $T^{-1}$ is a non-zero natural transformation $B_{fin} \to id_{fin}$.
However, here "natural" is understood in the formal sense of category theory. Could it be possible that for each $V$ there exists a linear map $S : V^{**} \to V$ such that $S \circ T = id$ which has a natural definition in some more intuitive sense? Again: No. First I would argue that if something has a short and elegant generic definition for all $V$, then it must be natural also in the formal sense. Okay, this is just a heuristic point of view and does not prove anything. But there is a more formal argument supporting the non-existence of an easily defined $S$.
Obviously $S$ can only exist if $T$ is injective. For infinite dimensional $V$ the injectivity of $T$ is proved by the axiom of choice which implies that $V^*$ separates the points of $V$ (i.e. that for each $x \in V, x\ne 0$, there exists $u \in V^*$ such that $u(x) \ne 0$). Indeed, this fact (assuming it for arbitrary $V$) is equivalent to the axiom of choice. See Andreas Blass' answer to Is the non-triviality of the algebraic dual of an infinite-dimensional vector space equivalent to the axiom of choice?
Therefore a universal easy definition of $S$ would substitute the axiom of choice in the proof of injectivity of $T$. In other words, $S$ would be something like a universal choice function - which is impossible. Actually any definition of $S$ will require the choice of a suitable basis of $V^{**}$. For finite-dimensional $V$ this can be overlooked since we do not need the full power of the axiom of choice; but even in that case we have to pick a basis $b_1,\ldots, b_n$ of $V$ and can then construct the dual and bidual bases of $V^*$ and $V^{**}$.