You are talking about Root Mean Squared Error of Prediction (RMSEP).
It is fundamentally different than the $R^2$ value, and they are not related in the way you are hoping. Your $R^2$ value is the approximate amount of $y$-variance (dependent variable variance) explained by your $x$-matrix of covariates (independent variables). This is answering the question "how much variance can I explain with my given set of predictors?"
Your RMSEP (explained in this website on calibration) is the approximate error that your model will produce in predicting a future out-of-sample value. It is a metric used to answer "if I use my current model in the real-world, how much error will it produce while predicting?"
$R^2$ is used to determine how much variance a model explains. RMSEP is used to determine how well your model can predict out-of-sample values. They are not related.