Although the result is intuitive, I'm still not certain about inverse elements in $L$. For instance, if $K=\mathbb Q$ and $L=\mathbb Q(\sqrt2,\sqrt3,\sqrt5,\sqrt7)$, then why is $$\frac{1}{\sqrt2+\sqrt3+\sqrt5+\sqrt7}$$ a linear combination of $\{1,\sqrt 2, \sqrt 3, \sqrt 6, \dots, \sqrt{210}\}$?
Now, actually, I'm aware of the fact that in the case of extensions of $\mathbb Q$ with surds, we can compute the inverse: $$-185 \sqrt{2}+145 \sqrt{3}+133 \sqrt{5}-135 \sqrt{7}-62 \sqrt{30}+50 \sqrt{42}+34 \sqrt{70}-22\sqrt{105},$$ but this was painstaking to compute, is there an easy way to see why this holds for any field extension $L/K$?
It seems to me like you're asking two separate questions:
The first question has a simple answer: because $L$ satisfies all the axioms of a $K$-vector space. Indeed, if we have addition and scalar multiplication, that's it! Here, you can completely forget about the fact that $L$ is a field.
Once you know that $L$ is a $K$-vector space, you can compute its dimension to be $[L:K]$ and find a basis. Any linearly independent set of size $[L:K]$ is a basis and, armed with this information, you know abstractly that every element of $L$ can be expressed as a $K$-linear combination of this basis.
However, actually computing explicitly how a given element looks in terms of this basis is tedious, and there's no reason you should expect otherwise!
The other answers give procedures for carrying out this computation. But I want to stress: whether or not this computation is easy or hard has nothing to do with the much easier fact that $L$ is a $K$-vector space.