I'll just exploit/spell out what @quark67 already hinted at in their comment. If I was in your place I'd convert the .svg-files to .pdf-files and use \includegraphics then. There are many (free, online) tools for that.
I am quite sure that you can use a larger number than 0.45, but not 0.5. The reason is that the line break after the first \end{subfigure} causes a space which is inserted between the two subfigures. This means you have 0.5\linewidth + space + 0.5\linewidth, which does not fit into one line. You can prevent the space if you comment the linebreak, see code below.
The image is stolen from https://freesvg.org/3d-atom-model, I just needed an example.

\documentclass{article}
\usepackage{svg} % provides 'includesvg'
\usepackage{subcaption} % provides 'subfigure' and corresponding caption
\usepackage{showframe} % only for testing reasons, just kick it out
\begin{document}
\begin{figure}[htbp]
\centering
\begin{subfigure}[b]{0.5\textwidth}
\includesvg[width=\textwidth]{example}
\caption{Subfig 1.}
\label{sfig:Picture4}
\end{subfigure}% <- This will prevent adding a small space between the subfigures which causes the linebreak.
\begin{subfigure}[b]{0.5\textwidth}
\includesvg[width=\textwidth]{example}
\caption{Subfig 2.}
\label{sfig:Picture2}
\end{subfigure}
\caption{Caption.}
\label{fig:Pictures}
\end{figure}
\end{document}
Edit
As seen in the comments, the text doesn't scale together with the image. Therefore one could use \resizebox instead of the optional width argument of \includesvg, but this leads to unreadable small text. Maybe a combination of both could satisfy the requirements:
\begin{subfigure}[b]{0.5\textwidth}
\scalebox{0.6666}{\includesvg[width=1.5\textwidth]{example}}
\caption{Subfig 2.}
\label{sfig:Picture2}
\end{subfigure}
Here it is necessary that the factor in \scalebox's first argument is the multiplicative inverse of the factor before \linewidth.
Obligatory note: It is not the best style to use \scaleboxes for figures containing text because this leads to nonuniform font sizes in your document. The cleanest way to go would be using TikZ.