I was one of the supporters of TOML back when this decision was made. I might have been the first one to suggest it, but I don't remember exactly.
Basically, I wanted something that was (1) simple, (2) terse, (3) supported comments, and (4) supported recursive data structures. Requirement (1) eliminated YAML, requirement (2) eliminated XML, requirement (3) eliminated JSON, and requirement (4) eliminated INI. Of the remaining formats, TOML seemed to be the most popular and had the most traction, so I went with that.
This seems reasonable, but I'd like to add that XML, while certainly not designed as a config language, could be made much more terse by using SGML, the markup metalanguage XML is derived from and of which XML is a subset. SGML has additional constructs for short forms such as tag omission/inference and short references (custom Wiki syntax) targetted at authoring, whereas XML only admits canonical angle bracket markup syntax which is what makes XML verbose and cumbersome for edititing by hand.
Basically, I wanted something that was (1) simple, (2) terse, (3) supported comments, and (4) supported recursive data structures. Requirement (1) eliminated YAML, requirement (2) eliminated XML, requirement (3) eliminated JSON, and requirement (4) eliminated INI. Of the remaining formats, TOML seemed to be the most popular and had the most traction, so I went with that.