I'm not sure if this is your confusion.
pca$sdev^2 -> eigen values -> variance in each direction
pca$sdev^2/sum(pca$sdev^2) = proportion of variance vector
So they ARE related.
Edit: Just an example (to illustrate this relationship), if that'll help.
set.seed(45) # for reproducibility
# set a matrix with each column sampled from a normal distribution
# with same mean but different variances
m <- matrix(c(rnorm(200,2, 10), rnorm(200,2,10),
rnorm(200,2,10), rnorm(200,2,10)), ncol=4)
pca <- prcomp(m)
> summary(pca) # note that the variances here equal that of input
# all columns are independent of each other, so each should explain
# equal amount of variance (which is the case here). all are ~ 25%
PC1 PC2 PC3 PC4
Standard deviation 10.9431 10.6003 10.1622 9.3200
Proportion of Variance 0.2836 0.2661 0.2446 0.2057
Cumulative Proportion 0.2836 0.5497 0.7943 1.0000
> pca$sdev^2
# [1] 119.75228 112.36574 103.27063 86.86322
> pca$sdev^2/sum(pca$sdev^2)
# [1] 0.2836039 0.2661107 0.2445712 0.2057142