Each person has to fulfil the formal requirements individually. The requirements don’t refer to “a couple”, only “an alien”.
A Non O-A visa can only be applied for at the embassy/consulate that serves your permanent residence. You both can apply with proof of income, but for an extension of stay in Thailand you’ll need to prove funds individually anyway.
It could vary between immigrations. I’ve got several for free from the police (immigration) at the country side, but it’s not a huge cost anyway. Seen feedbacks on 200 and 300 baht.
If you’re willing to pay, you could look into Thai Privilege Visa as well. Diamond gives you 15 years at 2,5 million baht. Then you would be close to Non O retirement visa and further stay.
No you’re right she would have to cancel the Non O first and apply later inside or outside Thailand, but she can apply for VOA if the Non O is not processed in time.
As you’re Bulgarian, you’re entitled to purchase a 15 days visa on arrival at 2000 baht at the immigration in Thailand. You can get a 7 days extension denied stamp as well, so in total 22 days in Thailand before you re-enter and activate your Non O visa.
Just extension of stay based on marriage. For regular retirement visa all immigrations accept twelve consecutive transactions over sea of minimum 65K baht as proof of income.