To export people to a csv file or a spreadsheet, first navigate to your People page.
From your Home page, look for the People link in the main left nav underneath ORGANIZATION. If you don't see the People link, that means you aren't an administrator on your organization. You'll need to ask a teammate to give you an Org Admin or Tech role on your organization so you can see the People page.
Once there, click the "Add, Import, or Export" dropdown in the top right corner, then choose "Export Employees":
This export will reflect the People View you have chosen, so ensure you've selected the People View containing all of the people you want to export.