Threnodic Spell is a metamagic feat that allows your enchantment spells to work against undead.
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The Undead sorcerer bloodline lets your mind-affecting effects affect the undead who were formerly humanoid.
Undead bloodline sorcerer with Threnodic spell (using magical lineage and preferred spell to reduce the metamagic cost for a few core spells) would pretty much do the job. Or do you mean in general, how to make a good enchanter vs the PCs? Spell focus and greater spell focus, Charming trait, Persistent metamagic.
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If you mean Enchantress in the normal English meaning of the term, and not literally a female Wizard with school focus in Enchantment, then a mesmerist is a very solid choice for this - logically.
Mesmerists have the ability to use mind-effecting spells against targets that are mindless and/or immune to mind-effecting spells by 3rd level:
Psychic Inception: The hypnotic stare and its penalty can affect creatures that are mindless or immune to mind-affecting effects (such as an undead or vermin). The mesmerist can also partially affect such a creature with his mind-affecting spells and abilities if it's under the effect of his hypnotic stare; it gains a +2 bonus on its saving throw (if any), and if affected, it still has a 50% chance each round of ignoring the effect. Ignoring the effect doesn't end the effect, but does allow the creature to act normally for that round.
This is a more general option than the others listed, but makes for quite an effective one. Additionally their entire class is focused on an enchantress-like character, it should fit really well. For a cult leader, there is even an archetype:
But for this specific character, there's an undead specific one that might be more appropriate:
Which also gives you mind-controlling the undead:
At 1st level, a spirit walker can affect undead creatures with his hypnotic stare as the psychic inception bold stare ability. This allows him to affect only undead; he must actually choose the psychic inception bold stare improvement if he wants to also affect other mindless creatures. At 3rd level when the spirit walker uses this ability, undead targets don't receive a saving throw bonus (if they did to begin with), have only a 25% chance of ignoring the spirit walker's mind-affecting spells and abilities, and no longer need to be under the spirit walker's gaze to be affected. At 5th level, when the spirit walker uses his mind-affecting spells and abilities, they affect all undead normally, with no chance of failure.
Or if you're going the wizard route, I'd suggest the Manipulator subschool for an Enchantment-specialist wizard (assuming the goal is charm/persuasion and not outright dominatation/mind-control, in which case I would suggest Controller instead). Charming, Domineering, Magical Lineage traits. Spell Focus/Greater Spell Focus, Persistent Spell, Focused Spell, Spell Penetration/Greater Spell Penetration (and/or make her an elf for the Elven Magic racial ability), Threndodic Spell, Preferred Spell. Obviously needs Craft Magic Arms and Armor if she can craft items that put off a mind fog effect. Int-boosting item, maybe headband of seduction or a circlet of persuasion. May make one of the lesser enchanters a bard for the 3rd-level bard spell Arcane Concordance if you want to boost her DCs further. For the Domineering trait and the Preferred Spell feat, you have to select a single spell. Since the enchantress is presumably most interested in undead humanoids, Charm Person for both would work. Otherwise you may want to put Preferred Spell in Charm Monster (or you could take it twice and do both).
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If you're going psychic casting, I'd go Psychic instead of Mesmerist. The Mesmerist ability can be used all day, but that 25/50% chance to ignore your enchantment every round hurts. The Psychic can take Will of the Dead phrenic amplification and make any mind-affecting spell (not just enchantment school, but also divinations, necromancy, and illusions) affect an undead. The only limit is your phrenic pool will limit you to twice a day at low levels, but if you stick it you don't have to worry about them being uncharmed half the time.
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There is a Dirge Bard archetype that is very useful in controlling undead.
I have a similar idea, she is the main pro/antagonist for my campaign, but she is a vampire with spellcaster levels as above. She uses the enchantment spells to make her victims forget about the feeding portions of the evening, and uses her society/club as a way to influence the powerful and wealthy. She has mostly bards as her acolytes, whether dirge bards or Negotiator bards specializing in Oratory.
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If you're going psychic casting, I'd go Psychic instead of Mesmerist. The Mesmerist ability can be used all day, but that 25/50% chance to ignore your enchantment every round hurts. The Psychic can take Will of the Dead phrenic amplification and make any mind-affecting spell (not just enchantment school, but also divinations, necromancy, and illusions) affect an undead. The only limit is your phrenic pool will limit you to twice a day at low levels, but if you stick it you don't have to worry about them being uncharmed half the time.
If you want consistency, I'd say it'd be better to go Spirit Walker mesmerist. At 5th level you always get all mind-affecting effects and spells off without any failure chance, an infinite number of times per day. Given that this is a 12th level character, I'd say that's better :)