I am assuming by "Mormon Underwear" you are referring to the Temple Garment. The Temple Garment is considered extremely sacred to members of the Church of Jesus Christ of Latter-day Saints and is not generally discussed in casual conversation or shown to those outside of the faith.
The Garment is received after one is washed and anointed in the Temple, in a ceremony similar to the one found in Leviticus 8 in the Old Testament. This ordinance is usually administered to those preparing to leave on missions ( usually ages 19 to 25), those preparing to be married in the temple, or to converts one year or more after their baptism. Church members who do not fall under one of these categories are usually recommended by their Bishop to receive it in their late 20's. Once receiving their washing and anointing, they are obligated to wear the Garment throughout their lives because of certain covenants they have made in the Temple.
The Garment serves to remind the wearer of the covenants they have made with God. It serves as an outward expression of an inward commitment to follow Jesus Christ, as a sort of protection, and as a promoter of modesty. Also, as Mormons have an all-lay ministry, the Temple Garment is considered a sort of 'priest's robe', just as some other religions minsters or pastors wear a special collar or robe to signify their authority to preach.
In short, there is no set age. The youngest age someone might start wearing the garment is 18, but only if they are leaving on a mission or getting married. Most who do not serve missions or marry young begin wearing it in their late 20's, and most converts do within a year or two of their baptism.
You can learn more about the Temple Garment at the "Related Links" below.
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The garment is a reminder of the covenents (promises) made to God in the Temple. Prerequisites for going to the temple to make these covenents are to be an adult, member of the church for at least a year, and to be recomneded by your bishop (which is the pastor of the congregation) as one who has is living a virtuous life.
If you mean the white garments it is because white is the purest colour and so we wear it when we are being baptised or are going to the temple. :)
Another answer:
The garments (the underclothes) that worthy members of the LDS (Mormon) Church wear do so as a reminder of special sacred covenants they have made between them and God in an LDS Temple. The covenants are not secret, but sacred covenants that are talked about primarily in The Bible.
The Temple Garment, or Garment of the Holy Priesthood, was introduced as part of the washing, annointing, and endowment ceremony of the Church of Jesus Christ of Latter-day Saints (the "Mormon" church) by 1842 (when the full endowment was introduced), but perhaps as early as 1836 (when the washing and annointing was first introduced).
Most do yes. The only ones who tend not to are the ones who question their own worthiness or commitment to the faith. To LDS it is as natural as wearing anything else.