If you already have a retirement visa for Thailand and I assume you have already met all the requirements for a retirement visa then there really wouldn't be any advantage in switching to the DTV.
And yes you are correct that the DTV is intended for people who wish to live in Thailand long term and work remotely but receive thier income from a source outside Thailand.
The DTV allows you to stay in Thailand up to 5 years at up to 180 days at a time.
You may need to research age care / disability homes and facilities specifically aimed at foreigners as that maybe your wife's only hope with her English language skills..
I believe these exist in Thailand but there are not many and the company would need to sponsor a working visa for your wife.
It's a long shot but at best but worth some investigation.
Or your wife may need to consider a career change to English language teaching as that's one of the few job opportunities available in Thailand.
But she would need to gain some kind of teaching qualification before attempting to find a job and again a work permit would need to be sponsored by any school willing to hire her..
There are many international shipping and removalist companies and all should be able to provide a estimate of the cost if you know what you want to send and most can provide delivery to your overseas address.
Air freight will be quickest of course but very expensive.
Shipping by sea a cheaper option but very slow..
You need to contact some companies for cost estimates.
Keep in mind when calculating your departure date that your arrival day is counted as day 1 of your first 60 days regardless of the time of day you arrive