Is there any foreseeable issue with using multiple passports to exit and re-enter Thailand?
For example, once I've exceeded the 2 annual land borders, can I simply exit at a border and then return on a second passport?
Answer summary
It is generally not allowed to switch between multiple passports when exiting and re-entering Thailand at land borders. You must leave Thailand using the same passport you used to enter. The only exception to switch passports is when traveling by air; that way, you can use a different passport for re-entry. Additionally, be aware that other countries you visit, such as Myanmar, may also require you to exit using the same passport with which you entered.
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As people pointed out you can ONLY switch passports by flying out and back into the country you can't do it by land..
You have to leave the country on the same passport you entered it with, and you can only switch by air, meaning you can't passport switch at land borders.
However, if you fly between countries there's no issue with multiple passports - you can switch.
I think there would be an issue with the country that you’re going to, Myanmar for example, would require you to exit their country using the same passport with which you entered. Then the Thai passport control would check your stamps in that passport.
I only have one passport so I don’t know personally but I briefly read a post of a friend of mine who had a similar issue.