If you place the image at (33.5,0.322), this will be the appropriate coordinate within the picture. This won't affect the placement of the image within the page - the coordinates are internal to the tikzpicture.
That is, you can do something like this:
\begin{tikzpicture}
\node[anchor=south west,inner sep=0] (image) at (33.5,0.322) {\includegraphics[width=0.9\textwidth]{example-image-a}};
\draw[red,ultra thick,rounded corners] (34,0.922) rectangle (34.7,1.722);
\end{tikzpicture}

You obviously don't want to set x and y here. At least, not in the way you are doing since that is specifically designed to set up the 0-1 coordinates.
Perhaps you want to adjust them something like this:
\newlength\iwidth
\newlength\iheight
\settoheight\iheight{\includegraphics[width=0.9\textwidth]{example-image-a}}
\settowidth\iwidth{\includegraphics[width=0.9\textwidth]{example-image-a}}
\begin{tikzpicture}[x=\iwidth/66.27,y=\iheight/1.457]% 1.779-0.322=1.457; 99.77-33.5=66.27
\node[anchor=south west,inner sep=0] (image) at (33.5,0.322) {\includegraphics[width=0.9\textwidth]{example-image-a}};
\draw[red,ultra thick,rounded corners] (34,0.922) rectangle (34.7,1.722);
\draw[blue,ultra thick] (33.5,0.322) rectangle (99.77,1.779);
\end{tikzpicture}

Complete code:
\documentclass{article}
\usepackage{tikz}
\begin{document}
\newlength\iwidth
\newlength\iheight
\settoheight\iheight{\includegraphics[width=0.9\textwidth]{example-image-a}}
\settowidth\iwidth{\includegraphics[width=0.9\textwidth]{example-image-a}}
\begin{tikzpicture}[x=\iwidth/66.27,y=\iheight/1.457]% 1.779-0.322=1.457; 99.77-33.5=66.27
\node[anchor=south west,inner sep=0] (image) at (33.5,0.322) {\includegraphics[width=0.9\textwidth]{example-image-a}};
\draw[red,ultra thick,rounded corners] (34,0.922) rectangle (34.7,1.722);
\draw[blue,ultra thick] (33.5,0.322) rectangle (99.77,1.779);
\end{tikzpicture}
\end{document}