Hi Neil,
I also just moved to Spain (Fuerteventura actually, so Canaries) from Germany and I have been using bunq as my main bank-account in Germany for the last 6 months so I know the up's and down's of European IBAN's pretty well.
In short: yes, theoretically no company is allowed to send you away with your Dutch IBAN. In Germany I did argue with some companies and wrote e-mails with the appropriate informations (links etc.) and in like 99% of the cases I got it all settled and could and did use my bunq account as my main account and I also actually canceled my old bank-account.
Now coming to another country it all kind of starts over again: I am only just learning Spanish so I am in no position to argue with companies, people or institutions (Policia Local or National for example). Also I noticed that Spain seems to be even more behind with the whole EU-IBAN thing than Germany. And I always thought that Germany was bad at this... It might cohere to the higher National Consciousness/Pride (promotion of your countries own products) that many companies still request a genuine Spanish IBAN.
I bowed to this now simply to get things rolling like ordering a Vodafone Internet-access cause otherwise I'd be in an even worse situation. But I will only use the Spanish IBAN like a throw-away Email Account and simply just forward payments from there (if any) to my bunq account or transfer some money to that account just to pay some fees or to make direct-debits work to verify accounts or so.
This is not what I actually want to do and it will also cost extra money but for now I don't see any real alternatives other than going into an argument and standing your ground but that's only workable (in my opinion) when you're fluent in Spanish.
I would be interested in your experiences though and your feedback. Maybe we can keep the discussion alive with informations from time to time or start an own thread for Spain in English for experiences with bunq in España!