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Hi and welcome to the Forum.

Once your fiancée has her UK spouse visa, she will be entitled to work in the UK; she will be liable for UK tax from the date she arrives in the UK; the UK Gov has a website with a mass of data on the subject; this will take you there.

Hope this helps.

Cynic
Expat Team

1) From the earnings perspective you need to establish a taxable structure before you can invoice for a service.
2) NI number is a unique lifetime number used to track employee payments into NI.
3) The tax reference will be found on the documents issued by HMRC once there are workable taxes. Reference types depend on your professional status.
4) For you both to start your activity you have options. Mostly choose between becoming a sole trader (with or without VAT registration), or setting up a ltd company (same note on VAT). Ltd companies are better set up through an accounting company. Accounting costs might be higher (say 50 to 150 pm) but allow dual directorship, employee statuses, shareholding etc), and potentially visas.
I hope it helps a bit. Best of luck with your new adventure.