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Line an 8-inch square baking pan with parchment paper, leaving a 2-inch overhang on all sides. Lightly coat pan with cooking spray. Stir together sugar, condensed milk, and whole milk in a medium saucepan. Cook over medium-low, stirring constantly, until a candy thermometer registers 238°F, about 16 minutes. Transfer sugar mixture to the bowl of a stand mixer fitted with a paddle attachment.
Add white chocolate, butter, and vanilla to stand mixer bowl; beat on low speed until white chocolate and butter are melted, about 1 minute. Increase mixer speed to medium, and beat until thickened and no longer shiny, 5 to 6 minutes. Pour into prepared pan; gently tap bottom of pan on counter until top is an even layer. Let cool, uncovered, at room temperature until firm, at least 2 hours or up to 12 hours. Remove from pan using parchment paper overhang as handles. Cut into 64 (1-inch) squares.