Consider starting your company together with someone who has experience that complements your own (e.g. marketing, sales, or organisational skills). It's difficult to replicate years of learning without devoting years to it.
Some companies (particularly tech firms) impose restrictions on the ownership of ideas that are generated whilst you work at the company so check first to make sure the MVP doesn't belong to your employer already!
Is it ethical to reach out to the president/business/marketing team to work with them and learn how a business is ran?
If learning how a business is run benefits you in your current position, yes.
If you are reaching out in your private time and asking the individuals to assist you in their private time, yes.
If your employer is supportive of personal development even when this doesn't benefit them directly, yes.
If you want your employer to pay you to learn things that don't help the company and will lead to you leaving, no.
Should I tread lightly or not ask for experience where I work?
If you give the impression that what you are asking for may lead to you leaving your current job then expect the people you reach out to to be conflicted.
An alternative approach would be to look for a secondment or apply internally for a job in that department in order to learn by doing. If you can make a case for how you can contribute then this benefits both you and your employer. Note that this could still be interpreted as an early sign that you may leave, so it is your read of the culture at you workplace that is key.