You need to perform a string comparison with the expansion of \@currenvir against itemize. \ifthenelse with the \equal operator does this, but you're short a magic \makeatletter...\makeatother wrapper (see What do \makeatletter and \makeatother do?).
Consider the post Why is the ifthen package obsolete?, I've used the e-TeX \pdfstrcmp to perform a string comparison that is expandable below. If the (numeral) result is 0, we have a match, otherwise it's non-zero:

\documentclass{article}
\makeatletter
\newcommand{\head}[1]{%
\ifnum\pdfstrcmp{\@currenvir}{itemize}=0
\textbf{#1}% Inside itemize
\else
\textit{#1}% Not inside itemize
\fi
}
\makeatother
\begin{document}
\begin{itemize}
\item \head{First} item
\end{itemize}
\begin{enumerate}
\item \head{Second} item
\end{enumerate}
\end{document}
The above usage should work for nested itemize as well.
You can also use the following \ifx conditional:
\makeatletter
\def\specialenvironment{itemize}
\newcommand{\head}[1]{%
\ifx\@currenvir\specialenvironment
\textbf{#1}% Inside "special environment"
\else
\textit{#1}% Not inside "special environment"
\fi
}
\makeatother
Note also the frequent use of %. For the motivation, see What is the use of percent signs (%) at the end of lines?
\makeatletter-\makeatother. – Bernard May 02 '15 at 17:14