You can measure the length of the contents within the \langle-\rangle and position \varsigma(s) accordingly:

\documentclass{article}
\usepackage{mathtools}% http://ctan.org/pkg/amsmath
\newlength{\templen}
\settowidth{\templen}{$1^{-s} + 2^{-s} + 3^{-s} + \cdots$}
\begin{document}
\begin{align*}
P[E_{m}] &= P[m] + P[2m] + P[3m] + \cdots \\
&= \frac{1}{\varsigma(s)} \langle m^{-s} + (2m)^{-s} + (3m)^{-s} + \cdots \rangle \\
&= \frac{1}{\varsigma(s)} \langle
\hspace*{.5\templen}\mathclap{\underbrace{1^{-s} + 2^{-s} + 3^{-s} + \cdots}}\hspace*{.5\templen} \rangle m^{-s} \\
&= \frac{1}{\varsigma(s)} \langle
\hspace*{.5\templen}\mathclap{\varsigma(s)}\hspace*{.5\templen} \rangle m^{-s} \\
&= m^{-s}
\end{align*}
\end{document}
For consistency I've spaced the \underbrace inside a \mathclap as well, since there is otherwise a minor misalignment.
The idea behind this approach is to step halfway into the expected width, then use \mathclap to place content in math-mode, centered in a zero-width box, and then complete the width-adjustment with another step the remaining half-width.
You can also mark the position on the page and calculate distances using the savepos module of zref:
\documentclass{article}
\usepackage{mathtools}% http://ctan.org/pkg/amsmath
\usepackage{zref-savepos}% http://ctan.org/pkg/zref
\makeatletter
% \zsaveposx is defined since 2011/12/05 v2.23 of zref-savepos
\@ifundefined{zsaveposx}{\let\zsaveposx\zsavepos}{}
\makeatother
\newcounter{hposcnt}
\renewcommand*{\thehposcnt}{hpos\number\value{hposcnt}}
\newcommand*{\SPl}{% set left position
\stepcounter{hposcnt}%
\zsaveposx{\thehposcnt spl}%
}
\newcommand*{\SPr}{% set right position
\zsaveposx{\thehposcnt spr}%
}
\makeatother
\begin{document}
\begin{align*}
P[E_{m}] &= P[m] + P[2m] + P[3m] + \cdots \\
&= \frac{1}{\varsigma(s)} \langle m^{-s} + (2m)^{-s} + (3m)^{-s} + \cdots \rangle \\
&= \frac{1}{\varsigma(s)} \langle
\SPl\underbrace{1^{-s} + 2^{-s} + 3^{-s} + \cdots}\SPr \rangle m^{-s} \\
&= \frac{1}{\varsigma(s)} \langle
\makebox[\dimexpr\zposx{\thehposcnt spr}sp-\zposx{\thehposcnt spl}sp]{$\varsigma(s)$} \rangle m^{-s} \\
&= m^{-s}
\end{align*}
\end{document}
It requires you to mark the left and right position using \SPl and \SPr, and then immediately use it to calculate the difference between the points (before setting another left/right mark).
\templenis96.57271pt, so you could get by using100ptand therefore leave a50ptjump on either side. However, if you don't know the width of something you have to measure it first. One could, of course, place labels to mark the horizontal location and space the placement automatically... – Werner Oct 08 '13 at 22:07