1. Quick solution
First, let me answer your question in short: feel free to use \v{e}, \'\i and \={\"u} to typeset ě, í and ǖ. You don't need pinyin package for this. And pinyin package itself is just a shortening for these accents.
2. A better implementation
Honestly, pinyin package on CTAN is not at all well implemented. It is dangerous to redefine, for example, \mu as pinyin since it is a Greek letter!
Here is a much better implementation of pinyin in Chinese, by 蒋 (ID: pointer) from CTeX forum, a Chinese TeX community:
\documentclass{article}
\usepackage[UTF8]{ctex}
% Definitions of Pinyin
\makeatletter
\def\py@yunpriv#1{%
\if a#1 10\else
\if o#1 9\else
\if e#1 8\else
\if i#1 7\else
\if u#1 6\else
\if v#1 5\fi\fi\fi\fi\fi\fi0
}
\def\py@init{%
\edef\py@befirst{}%
\edef\py@char{}\edef\py@tuneletter{}%
\def\py@last{}%
\def\py@tune{5}%
}
% Usage:
% \pinyin{Hao3hao3\ xue2xi2} (好好学习)
\def\pinyin#1{%
\edef\py@postscan{#1}%
\py@init
% scan
\loop
\edef\py@char{\expandafter\@car\py@postscan\@nil}%
\edef\py@postscan{\expandafter\@cdr\py@postscan\@nil}%
\ifnum 0 < 0\py@char
\edef\py@tune{\py@char}%
\py@first \py@tuneat\py@tuneletter\py@tune \py@last\kern -4sp\kern 4sp{}\py@init
\else
\ifnum\py@yunpriv\py@char > \py@yunpriv\py@tuneletter
\edef\py@tuneletter{\py@char}\edef\py@first{\py@befirst}\def\py@last{}%
\else
\edef\py@last{\py@last\if v\py@char\"u\else\py@char\fi}%
\fi
\edef\py@befirst{\py@befirst\if v\py@char\"u\else\py@char\fi}%
\fi
\ifx\py@postscan\@empty\else
\repeat
}
\let\py@macron \=
\let\py@acute \'
\let\py@hacek \v
\let\py@grave \`
%% \py@tuneat{Letter}{tune}
\def\py@tuneat#1#2{%
\if v#1%
\py@tune@v #2%
\else
\if i#1%
\py@tune@i #2%
\else
\ifcase#2%
\or\py@macron #1\or\py@acute #1\or\py@hacek #1\or\py@grave #1\else #1%
\fi
\fi\fi
}
\def\py@tune@v#1{{%
\dimen@ii 1ex%
\fontdimen5\font 1.1ex%
\rlap{\"u}%
\fontdimen5\font .6ex%
\ifcase#1%
\or\py@macron u\or\py@acute u\or\py@hacek u\or\py@grave u\else u%
\fi
\fontdimen5\font\dimen@ii
}}
\def\py@tune@i#1{%
\ifcase#1
\or\py@macron \i\or\py@acute \i\or\py@hacek \i\or\py@grave \i\else i%
\fi
}
\makeatletter
% End of pinyin
\begin{document}
女人 \pinyin{nv3ren2}
木头 \pinyin{mu4tou5} --- $\mu$ % no conflicts
韵母 \pinyin{a1\ i3\ u4\ v2}
\end{document}

3. My final advice
Nowadays, we sugguest XeTeX with xeCJK for CJK typesetting. XeTeX is a Unicode TeX engine, then you can use ě, í and ǖ in the source code directly, with help of a good GUI input pad. The example above can be changed to:
% XeLaTeX needed
\documentclass{article}
\usepackage[UTF8]{ctex}
\begin{document}
女人 nǚrén
木头 mùtou --- $\mu$
韵母 ā ǐ ù ǘ
\end{document}
Don't use pdfLaTeX or latex with CJK to compile this. Since some of the vowels are handled by CJK but the fonts are full-width (badly designed), the result may be strange without XeTeX. Of course, if you don't need CJK ideograms, you can use inputenc package for the pinyin vowels.
4. A new xpinyin package is available
Qing Lee (李清) wrote a new xpinyin package to typesetting pinyin semi-automatically.
\documentclass{article}
\usepackage{xeCJK}
\usepackage{xpinyin}
\setmainfont{CMU Serif}
\setCJKmainfont{SimSun}
\begin{document}
\xpinyin*{汉语拼音示例}
\pinyin{nv3hai2zi}
\end{document}