I've gone ahead and scoped out your settings, and upon performing a test checkout with the product Camiseta Viena Dream (pack 6 tallas), both from the tax-override region of Santa Cruz de Tenerife and the tax-included region of Barcelona. Neither of these options actually charged the customer tax for the product. You can see the results below:
Looking into this further, it appears that your products need to be set up to enable charging tax. This will then add the tax option to the checkout process for all regions in Spain except for those you have already set up a tax override for.
To do this, you'll want to select all of your products for use, and then add the option in the product bulk editor. I've gone ahead and made a video demonstrating this process within my own test store in this set of images below. Just make sure you click the blue text that states "Select all 50+ products from your store" to the right of the select all button once you've hit the check boxes if it appears, as this step is not featured here. The reason for this is that selecting all on a page will only apply to the 50 products seen there, so if you have a catalogue bigger than that, you'll want to save time by telling it to include all other pages:
Note: You can speed the process up by dragging the bottom of the selection box in any row to encompass all products on this page, then clicking once. This will enable the option for all 50 products in that page. You will also need to save each page of 50 products before moving onto the next using the arrow icons on the bottom of the page.
That will have you all set! Give that a shot and let me know if issues persist. 🙂