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For best results, launch with Gamescope, so apps can launch inside of Steam. You may want to tweak the command line options depending of your setup.

Create an icon with this desktop file, add it to ~/.local/share/applications/, and link it in ~/.config/autostart/:

~/.local/share/applications/steam-big-picture.desktop

[Desktop Entry]
Name=Steam Big Picture Mode
Comment=Start Steam in Big Picture Mode
Exec=/usr/bin/env WLR_RENDERER_ALLOW_SOFTWARE=1 gamescope -e -W 1920 -H 1080 -f -g --expose-wayland --backend sdl -- /usr/bin/steam -tenfoot -steamdeck
Type=Application
Icon=steam

You can use sdl or wayland for the backend option.

/usr/share/wayland-sessions/steam-big-picture.desktop

[Desktop Entry]
Name=Steam Big Picture Mode
Comment=Start Steam in Big Picture Mode
Exec=/usr/bin/gamescope -e --expose-wayland --backend wayland --prefer-vk-device --disable-layers -- env WLR_RENDERER_ALLOW_SOFTWARE=1 steam -tenfoot -steamdeck
Type=Application

You can use drm or wayland for the backend option.