For a special class of numbers, that many irrational numbers are, there is a certain measure of "complexity" (I say "many" in a loose everyday sense, it turns out that almost all irrational numbers are in fact not in this class). This class is called the Algebraic Numbers, and these are the set of numbers that are solutions to some polynomial equation with integer coefficients. For example, \sqrt{5} and 7^{1/5} are algebraic as they are roots of x^2-25, x^5-7 respectively. We say an algebraic number is of degree n if n is the smallest degree a polynomial must be to have the number as a solution. In our examples, the numbers are of degree 2 and 5 respectively. We can regard lower degree algebraic numbers as "simpler" and "less irrational" in some sense to higher degree algebraic numbers. For example, the set of algebraic numbers of degree 1 is the set of solutions to ax + b = 0, where a and b are integers, ie the rational numbers. It is only from degree 2 onwards we "step up" a level and get to irrational numbers (or imaginary numbers).
If the number is not the solution of any polynomial with integer coefficients, we call them transcendental numbers (they "transcend" algebraic equations). Since all rational numbers are algebraic numbers (of degree 1), all real transcendental numbers are immediately irrational, but not all irrational numbers are transcendental. Examples of numbers in the latter class are \pi and e. From this we can already reason that these two constants are "more complex" than the other irrational numbers mentioned here previously, so your question is not a foolish one to ask. However, there is no longer a quantitative comparison like we had for algebraic numbers.
e comes about very naturally when doing Calculus, Differential Equations or Complex Analysis (I've probably missed others), and then one finds by investigation of the exponential function that it has a period of 2\pi i. When \pi finds a reason to pop up somewhere, often its because the exponential function has found a way to pop up somewhere, often disguised as a trigonometric function or some other alias. For example, a circle in the complex plane is traced out by a full period of e^{it}, and because we call this period 2\pi i, we've already linked \pi into all of our circular geometry. So in a purely subjective sense, I would say that e is the more fundamental number while \pi arises as a by-product while dealing with e.