Various latter day Rabbonim and mechanchim speak about early training as a means to create 'רגילות במצוות' - i.e. the means of making mitzvos habitual and second nature to the child. As the adage goes, "ההרגל על כל דבר שלטון" – “The habit of something holds sway”. (See See מדרש שמואל פרקי אבות א:יד who quotes ר"י ן' שושן ז"ל). Indeed this is how the מצודות דוד on משלי כב:ו interprets the pasuk of חֲנֹ֣ךְ לַ֭נַּעַר.
As a result this sense of רגילות is one of the underlying reasons why we train children from a young age in the practise of מצוות.
Quite a few examples have been listed already - but perhaps two more can be listed that show how this sense of routine manifests itself in both the positive and negative sense.
Both of them centre around your point about getting them "used to Yom Kippur"
in מסכת יומא פב we are told that whilst ordinarily children under בר\בת מצוה do not fast on יום כיפור, they should do so a year or two before they come of age so that they become accustomed to fasting.
The Mishna there writes:
התינוקות אין מענין אותן ביוה"כ אבל מחנכין אותן לפני שנה ולפני שנתיים בשביל שיהיו רגילין במצות
With regard to the children, one does not afflict them by withholding food on Yom Kippur; however, one trains them one year before or two years before they reach majority, by means of a partial fast lasting several hours, so that they will be accustomed to fulfill mitzvot.
(Sefaria translation & notation)
Meanwhile the גמרא in מסכת עירובין מ speaks about making קידוש in shul on יום כיפור night. It notes that one cannot recite קידוש on a cup of wine without tasting it immediately after the ברכה has been said (In fact, רש"י ד"ה ליתביה לינוקא adds that to do so is a גנאי, a disgrace.). Due to the fact that it is a fast day we obviously would not be able to drink from the cup. Thus, the גמרא suggests offering it to a minor to drink, thereby allowing for the potential to say it. However the גמרא concludes – "דילמא אתי למסרך" – “Perhaps he (the child) might become used to it”. As רש"י explains, should the child drink the wine, he might become acclimatised to such a practise even after he becomes בר מצוה. Therefore, we see from this גמרא that anything that might come to create a negative inclination in the child must be avoided too.