Let $V$ be a finite-dimensional vector space. It is well known that there is a natural isomorphism between $V$ and its double dual $V^{\ast\ast}$ defined by $T(x)(f)=f(x)$ for every $x\in V$ and $f\in V^\ast$.
However, I am unable to write down a definition of $T^{-1}$ directly without any reference to $T$ and without picking any basis. Thus it seems to me that the isomorphism between the two vector spaces is not really so natural if we look at the direction from $V^{\ast\ast}$ to $V$.
Is it possible to define $T^{-1}$ in a direct and natural way? If not, does this asymmetry in the easiness of definition have any significance in linear algebra or other branches of mathematics?
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:
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:
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 $V^{**}$.