Minimal example (the problem is obvious):
\documentclass[]{report}
\makeatletter
\def\@makechapterhead#1{
\vspace*{-5.0em}
{\parindent \z@ \normalfont
\interlinepenalty\@M
\LARGE{0\thechapter}
\par\vspace{0.25cm}
\flushleft\MakeUppercase{#1}}
\par\vspace{3.5em}
}
\makeatother
\begin{document}
\chapter{First Chapter}
\setcounter{chapter}{9}
\chapter{Tenth Chapter}
\appendix
\chapter{Appendix A}
\end{document}
Edit: I forgot to mention something important. Only the displayed chapter numbers should have 0s in front of them, not definitions, theorems, etc. That is: Chapter 01, Definition 1.1., etc.


