The trouble with the terminology of 'inner' and 'outer' functions is that it's notation-dependent. It assumes the function composition is written as f(g(x)). As you've noted, it doesn't work like that for exponents.
I find it easier to think in terms of order of evaluation. That is, if we were given a numeric value of x, and had to evaluate the function value on a calculator, which function would we do first, which second, and so on if necessary. There is only one way that can be done, so it's not notation-dependent. We can call the functions first, second, third etc, rather than inner and outer.
If evaluating ##e^{4e^x}## for a given numeric value of x, we'd have to evaluate the expression in the exponent first, so that is the first function. We then need to exponentiate the result of that, and that exponentiation is the second function.
This approach mirrors how things are written if we use function composition notation, like ##(f\circ g)(x)##. In that notation, we work from right to left in applying the functions, so the rightmost function is first, the next-rightmost second, and so on.