Hello Anthony, I'm Keith and happy to help you with your question.
If you work full time for the NHS, and often part time too, you will almost certainly be paid under PAYE arrangements and have tax and national insurance contributions deducted at source.
If you operate through a limited company please remember that if you are a Director of the company then you are an employee per se and must also be paid under PAYE arrangements set up by the company. If you pay yourself by means of dividends these would be grossed up to the highest rates of personal taxation appropriate and furthermore the dividends are not allowable against the company's Corporation tax assessments whereas salary drawn is so allowable.
If you go down the self employment route you must register with HMRC. Here is the HMRC guidance of the matter:
'How and when to register with HM Revenue & Customs (HMRC) It's important to let HMRC know that you're self-employed as soon as possible - even if you already fill in a Self Assessment tax return each year. If you don't tell them, you may have to pay a penalty.
You can let HMRC know about your self-employment by registering online for business taxes. You'll be asked for information about yourself and your business. HMRC will set up tax records for you using the information you provide, for example records for:
PAYE if you have people working for you
A Self Assessment Online account automatically will be set up for you at the same time, unless you say that you don't want one.'
Working this way will involve detailed book keeping, fairly simple, but necessary. You could always employ a sub-contractor to look after those matters for you.
On an estimated gross income of 96K you would pay tax on 86K (after your personal allowance of 10K) at 20% on the first GBP 31865 and 40% thereafter, about 32.5K. You will also be liable for NI contributions also. Your gross would, of course, be reduced by any professional subscriptions etc paid, but these are small beer. The greatest money spinner in tax avoidance is a private pension plan. You may make, including your employer's contribution, up to 100% of your income or 40K whichever is the lower.
You can see now that whichever way you turn you cannot avoid taxation. As Benjamin Franklin once famously quipped in life there are but two certainties, death and taxes!
I do hope I have thrown some light on your plans for you.