Mary Ann is not the same individual as Ann Skelton Cleveland. They are sisters who each married a man from the Cleveland family.
Sources
1850 United States Census Report. "United States Census, 1850," index and images, FamilySearch (https://familysearch.org/pal:/MM9.1.1/MZYG-3JF : accessed 12 Sep 2014), Mary Cleveland in household of John A Cleveland, Franklin county, part of, Franklin, Georgia, United States; citing family 8, NARA microfilm publication M432.
1860 United States Census Report. "United States Census, 1860," index, FamilySearch (https://familysearch.org/pal:/MM9.1.1/MZMX-9GM : accessed 09 Sep 2014), Polly Cleveland in household of John A Cleveland, Hartwell District, Hart, Georgia, United States; citing "1860 U.S. Federal Census - Population," Fold3.com; p. 485, household ID 746, NARA microfilm publication M653; FHL microfilm 803126.
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DNA Connections
It may be possible to confirm family relationships with Mary by comparing test results with other carriers of her mitochondrial DNA.
However, there are no known mtDNA test-takers in her direct maternal line.
It is likely that these autosomal DNA test-takers will share some percentage of DNA with Mary: