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War-era Cylon Centurions' psychology
All War-era Cylon Centurions have some parts of Zoe-R identity in their mainframe program. Sister Clarice Willow and Lacy Rand become aware of that and use it to fullfill their purposes (CAP: "The Heavens Will Rise", "Apotheosis").
Modern Cylon Centurions' psychology
At first sight, Modern Centurions exist only to obey orders given by Humanoid Cylons. Their purpose and existence are limited to humanoid closed guard and commando actions. Actually, according to Sharon Agathon, the thinking function exists but has been switched off by Cavil in order to prevent a rise of the machines (TRS: "Precipice").
Humanoid Cylons psychology
The humanoid models 1-8, built with the know-how and assistance of the Final Five, appear and behave human, even to the extent that they may feel experience life at times as humans do. Paradoxically, they also display a superhuman or inhuman capacity to display any feeling helpful toward deception and in service of atrocities.
Though they are resurrection-ready and therefor immortal, they have never been children or matured within a human social environment. Most have had no human social experience whatsoever. Even Caprica-Six and Eight Sharon Valerii, regarded with awe by others, experienced only a few years of life among humans at the most. The Cylons seem to lack even a theory for why humans do or feel as they do--not as the saga begins, at least. Their "Plan" for dealing with the fleeing unexpected survivors of their extermination attempt switches from one tack to the next. They base choices on what "Caprica" and Sharon Valerii have managed to learn, and that's not much, judging from the failure of New Caprica.
Yet these two appear to have been affected even by their brief experience, such that they feel the pull of desires and emotions they did not have before and arguably become addicted to them. The psychology of the Sixes and Eights at least is not entirely pre-fab or stable out of the box, in that they seem predisposed to life in human society, but born unwise to it, like pre-pubescent teens. Whether other models would opt for a human-like life, given sufficient experience of it, is less clear.
The Ones do seem to come from the box ill-equipped and dead-set against it, but then humans can be like that too, most often as infants. Conceivably Ones could adapt to living as a human, were they obliged to do so, as children always are. But being born with seniority, authority and no strong commitment to democracy, the circumstance does not arise.
Final Five psychology
The Final Five do not remember the lives from which they resurrected themselves two thousand years before, but they were born and raised from childhood in a society like humans. They are diverse, each an entirely human-seeming individual. Of course, they are not human, it seems reasonable to suppose that more or less they are.