With the GNOME Display Manager (GDM), you need to choose the session at the login screen. Although Trisquel Mini uses LXDM, I believe it must be similar.

If you have indeed chosen an Xfce session at the login screen, what is the exact problem you encounter? Have you tried launching Xfce from a terminal (one of those you obtain with Ctrl+Alt+F[1-6])? When I was using Xfce the command to run was start-xfce4.

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