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If the DNA error happened because of real world stuff, not magic, then the easiest way would be to "accidentally" provide a tissue sample or previous DNA test that was supposed to be Kathryn's but wasn't.
The tissue sample would be safest. For example, if there had been blood in Kathryn's car (there wasn't, as far as I remember), you could believe it was the driver's (Kathryn) then test it against the heart's DNA.
You later find out you were wrong, but you're still looking at a murder associated with your missing person. So, Kathryn may have picked someone up, something happens to the car, and she and the other person were attacked. Investigators don't know about the second person and assume the blood on the driver's side is Kathryn's.
So, to look innocent, you want a tissue sample that should have been Kathryn's but could have logically been that of a person travelling with her or otherwise around the car when it crashed or who came across it shortly after.*
If you have a DNA record (and why not? SB has everyone's fingerprints on record, so let's just up the police state factor, shall we?), you're going to have a hard time convincing investigators that you just happened to send the wrong record and that it just happened to match the anonymous heart found in the woods.
Well, if there'd been another missing person with a DNA record attached and it was the one sent, then it makes a certain sense - but there weren't any other missing people.
It screams deliberate frame up.
*Examples:
1) Claim Kathryn picked up a hitchhiker who was later murdered.
2) Claim Kathryn picked up two hitchhiker's, one of whom was a psychopath who had robbed at least one local (possibly had stalking tendencies).
3) Someone found the car after the accident and was murdered by a vagrant psychopath (who had committed robberies). Said psycho may have also injured/menaced Kathryn.
4) Given Kathryn's apparent mental condition, someone may try to prove she committed the murder while in a deranged state (in real life, without an identified victim and with the previous open and shut case having been proven dead wrong, there might be suspicion but the case would likely remain open and unsolved. I just wouldn't count on that in Storybrooke).
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